U.S. patent number 10,381,577 [Application Number 15/321,397] was granted by the patent office on 2019-08-13 for hetero-cyclic compound and organic light emitting device using the same.
This patent grant is currently assigned to HEESUNG MATERIAL LTD.. The grantee listed for this patent is HEESUNG MATERIAL LTD.. Invention is credited to Dae-Hyuk Choi, Jin-Seok Choi, Dong-Jun Kim, Joo-Dong Lee, Yun-Ji Lee, Jae-Yeol Ma, Han-Kook Oh, Geon-Yu Park.
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United States Patent |
10,381,577 |
Park , et al. |
August 13, 2019 |
Hetero-cyclic compound and organic light emitting device using the
same
Abstract
The present application provides a hetero-cyclic compound which
may significantly improve the lifetime, efficiency, electrochemical
stability, and thermal stability of an organic light emitting
device, and an organic light emitting device in which the
hetero-cyclic compound is contained in an organic compound
layer.
Inventors: |
Park; Geon-Yu (Osan-si,
KR), Oh; Han-Kook (Osan-si, KR), Lee;
Yun-Ji (Osan-si, KR), Ma; Jae-Yeol (Yongin-si,
KR), Kim; Dong-Jun (Yongin-si, KR), Choi;
Jin-Seok (Suwon-si, KR), Choi; Dae-Hyuk
(Yongin-si, KR), Lee; Joo-Dong (Seongnam-si,
KR) |
Applicant: |
Name |
City |
State |
Country |
Type |
HEESUNG MATERIAL LTD. |
Yongin, Gyeonggi-do |
N/A |
KR |
|
|
Assignee: |
HEESUNG MATERIAL LTD. (Yongin,
KR)
|
Family
ID: |
58108986 |
Appl.
No.: |
15/321,397 |
Filed: |
July 27, 2016 |
PCT
Filed: |
July 27, 2016 |
PCT No.: |
PCT/KR2016/008189 |
371(c)(1),(2),(4) Date: |
December 22, 2016 |
PCT
Pub. No.: |
WO2017/018795 |
PCT
Pub. Date: |
February 02, 2017 |
Prior Publication Data
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|
|
Document
Identifier |
Publication Date |
|
US 20170213988 A1 |
Jul 27, 2017 |
|
Foreign Application Priority Data
|
|
|
|
|
Jul 27, 2015 [KR] |
|
|
10-2015-0106063 |
May 11, 2016 [KR] |
|
|
10-2016-0057665 |
May 13, 2016 [KR] |
|
|
10-2016-0059084 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07D
495/04 (20130101); C07D 333/76 (20130101); H01L
51/0071 (20130101); H01L 51/50 (20130101); H01L
51/0074 (20130101); C07D 487/04 (20130101); C09K
11/06 (20130101); H01L 51/00 (20130101); C07D
209/82 (20130101); C07D 491/04 (20130101); C09K
11/025 (20130101); C07D 409/14 (20130101); H01L
51/0072 (20130101); H01L 51/0067 (20130101); C09K
2211/1044 (20130101); H01L 51/0081 (20130101); C09K
2211/1007 (20130101); H01L 51/0085 (20130101); C09K
2211/1059 (20130101); H01L 51/5016 (20130101); H01L
2251/552 (20130101); C09K 2211/1092 (20130101) |
Current International
Class: |
H01L
51/50 (20060101); C07D 209/82 (20060101); C07D
333/76 (20060101); C07D 495/04 (20060101); C09K
11/06 (20060101); C09K 11/02 (20060101); C07D
491/04 (20060101); C07D 487/04 (20060101); C07D
409/14 (20060101); H01L 51/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
|
|
|
3243820 |
|
Nov 2017 |
|
EP |
|
2009-267255 |
|
Nov 2009 |
|
JP |
|
2012-222268 |
|
Nov 2012 |
|
JP |
|
2013-16717 |
|
Jan 2013 |
|
JP |
|
2014-017494 |
|
Jan 2014 |
|
JP |
|
2016-51901 |
|
Apr 2016 |
|
JP |
|
2016-149473 |
|
Aug 2016 |
|
JP |
|
10-2014-0122929 |
|
Oct 2014 |
|
KP |
|
10-2011-0112098 |
|
Oct 2011 |
|
KR |
|
10-2013-0100236 |
|
Sep 2013 |
|
KR |
|
WO 2011/004639 |
|
Jan 2011 |
|
WO |
|
WO 2011/126224 |
|
Oct 2011 |
|
WO |
|
WO 2013/168534 |
|
Nov 2013 |
|
WO |
|
WO 2014/091958 |
|
Jun 2014 |
|
WO |
|
Other References
Bin, J.K. et al, "New sulfur-containing host materials for blue
phosphorescent organic light-emitting diodes," J. Mater. Chem.,
2012, vol. 22, pp. 21720-21726. cited by applicant .
Office Action issued in Korean Patent Application No.
10-2016-0057665, dated Oct. 5, 2016. cited by applicant .
Office Action issued in Korean Patent Application No.
10-2016-0059084, dated Aug. 8, 2016. cited by applicant .
Extended European Search Report for European Application No.
16830828.6, dated Jan. 17, 2019. cited by applicant.
|
Primary Examiner: Clark; Gregory D
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Claims
The invention claimed is:
1. A hetero-cyclic compound represented by the following Chemical
Formula 1: ##STR00296## in Chemical Formula 1, L1 and L2 are the
same as or different from each other, and each independently a
direct bond or a substituted or unsubstituted C.sub.6 to C.sub.60
arylene group, Ar1 is selected from the group consisting of a
substituted or unsubstituted pyridine group; a substituted or
unsubstituted pyrimidine group; a substituted or unsubstituted
triazine group; a substituted or unsubstituted quinoline group; a
substituted or unsubstituted quinazoline group; a substituted or
unsubstituted phenanthroline group; and a substituted or
unsubstituted benzoimidazole group, Ar2 is represented by any one
of the following Chemical Formulae 3 and 4, ##STR00297## in
Chemical Formulae 3 and 4, Y1 to Y4 are the same as or different
from each other, and each independently a substituted or
unsubstituted C.sub.6 to C.sub.60 aromatic hydrocarbon ring; or a
substituted or unsubstituted C.sub.2 to C.sub.60 aromatic hetero
ring, R1 to R7 are the same as or different from each other, and
each independently selected from the group consisting of hydrogen;
deuterium; a halogen group; --CN; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkenyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkynyl group; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkoxy group; a substituted or unsubstituted
C.sub.3 to C.sub.60 cycloalkyl group; a substituted or
unsubstituted C.sub.2 to C.sub.60 heterocycloalkyl group; a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group;
--SiRR'R''; --P(.dbd.O)RR'; and an amine group which is
unsubstituted or substituted with a C.sub.1 to C.sub.20 alkyl
group, a substituted or unsubstituted C.sub.6 to C.sub.60 aryl
group, or a C.sub.2 to C.sub.60 heteroaryl group, or two or more
adjacent groups combine with each other to form a substituted or
unsubstituted aliphatic or aromatic hydrocarbon ring, and R, R',
and R'' are the same as or different from each other, and are each
independently hydrogen; deuterium; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted
or unsubstituted C.sub.2 to C.sub.60 heteroaryl group.
2. The hetero-cyclic compound of claim 1, wherein Chemical Formula
3 is represented by any one of the following structural formulae:
##STR00298## in the structural formulae, X1 to X6 are the same as
or different from each other, and each independently NR, S, O, or
CR'R'', R8 to R14 are the same as or different from each other, and
each independently selected from the group consisting of hydrogen;
deuterium; a halogen group; --CN; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkenyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkynyl group; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkoxy group; a substituted or unsubstituted
C.sub.3 to C.sub.60 cycloalkyl group; a substituted or
unsubstituted C.sub.2 to C.sub.60 heterocycloalkyl group; a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group;
--SiRR'R''; --P(.dbd.O)RR'; and an amine group which is
unsubstituted or substituted with a C.sub.1 to C.sub.20 alkyl
group, a substituted or unsubstituted C.sub.6 to C.sub.60 aryl
group, or a C.sub.2 to C.sub.60 heteroaryl group, or two or more
adjacent groups combine with each other to form a substituted or
unsubstituted aliphatic or aromatic hydrocarbon ring, R, R', and
R'' are the same as or different from each other, and each
independently hydrogen; deuterium; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted
or unsubstituted C.sub.2 to C.sub.60 heteroaryl group, and m is an
integer of 0 to 8, and n, o, p, q, r, and s are each independently
an integer of 0 to 6.
3. The hetero-cyclic compound of claim 1, wherein Chemical Formula
4 is represented by any one of the following structural formulae:
##STR00299## in the structural formulae, X7 and X8 are the same as
or different from each other, and each independently NR, S, O, or
CR'R'', R15 to R18 are the same as or different from each other,
and each independently selected from the group consisting of
hydrogen; deuterium; a halogen group; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.2 to C.sub.60 alkenyl group; a substituted or
unsubstituted C.sub.2 to C.sub.60 alkynyl group; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkoxy group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.2 to C.sub.60 heterocycloalkyl group; a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group;
--SiRR'R''; --P(.dbd.O)RR'; and an amine group which is
unsubstituted or substituted with a C.sub.1 to C.sub.20 alkyl
group, a substituted or unsubstituted C.sub.6 to C.sub.60 aryl
group, or a C.sub.2 to C.sub.60 heteroaryl group, or two or more
adjacent groups combine with each other to form a substituted or
unsubstituted aliphatic or aromatic hydrocarbon ring, and R, R',
and R'' are the same as or different from each other, and each
independently hydrogen; deuterium; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted
or unsubstituted C.sub.2 to C.sub.60 heteroaryl group, and t is an
integer of 0 to 7.
4. The hetero-cyclic compound of claim 1, wherein Chemical Formula
1 is represented by any one of the following Chemical Formulae 5 to
10: ##STR00300## ##STR00301## in Chemical Formulae 5 to 10, the
definitions of R1 to R6, L1, and Ar1 are the same as those in
Chemical Formula 1, X1, X4, and X5 are the same as or different
from each other, and each independently NR, S, O, or CR'R'', R8,
R9, R12, R13, and R16 are the same as or different from each other,
and each independently selected from the group consisting of
hydrogen; deuterium; a halogen group; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.2 to C.sub.60 alkenyl group; a substituted or
unsubstituted C.sub.2 to C.sub.60 alkynyl group; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkoxy group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.2 to C.sub.60 heterocycloalkyl group; a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group;
--SiRR'R''; --P(.dbd.O)RR'; and an amine group which is
unsubstituted or substituted with a C.sub.1 to C.sub.20 alkyl
group, a substituted or unsubstituted C.sub.6 to C.sub.60 aryl
group, or a C.sub.2 to C.sub.60 heteroaryl group, or two or more
adjacent groups combine with each other to form a substituted or
unsubstituted aliphatic or aromatic hydrocarbon ring, R, R', and
R'' are the same as or different from each other, and each
independently hydrogen; deuterium; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted
or unsubstituted C.sub.2 to C.sub.60 heteroaryl group, and m is an
integer of 0 to 8, n, q, and r are each independently an integer of
0 to 6, and t is an integer of 0 to 7.
5. The hetero-cyclic compound of claim 1, wherein R1 to R6 of
Chemical Formula 1 are each independently hydrogen or
deuterium.
6. The hetero-cyclic compound of claim 2, wherein R8 to R14 of the
structural formulae are each independently hydrogen; deuterium; a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; or a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl
group.
7. The hetero-cyclic compound of claim 3, wherein R5 to R18 of the
structural formulae are each independently hydrogen; deuterium; a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; or a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl
group.
8. The organic light emitting device of claim 1, wherein Chemical
Formula 1 is represented by any one of the following compounds:
##STR00302## ##STR00303## ##STR00304## ##STR00305## ##STR00306##
##STR00307## ##STR00308## ##STR00309## ##STR00310## ##STR00311##
##STR00312## ##STR00313## ##STR00314## ##STR00315## ##STR00316##
##STR00317## ##STR00318## ##STR00319## ##STR00320## ##STR00321##
##STR00322## ##STR00323## ##STR00324## ##STR00325## ##STR00326##
##STR00327## ##STR00328## ##STR00329## ##STR00330## ##STR00331##
##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336##
##STR00337## ##STR00338## ##STR00339## ##STR00340## ##STR00341##
##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346##
##STR00347## ##STR00348## ##STR00349## ##STR00350## ##STR00351##
##STR00352## ##STR00353## ##STR00354## ##STR00355## ##STR00356##
##STR00357## ##STR00358## ##STR00359##
9. An organic light emitting device comprising: a positive
electrode; a negative electrode; and one or more organic material
layers provided between the positive electrode and the negative
electrode, wherein one or more layers of the organic material
layers comprise the hetero-cyclic compound of claim 1.
10. The organic light emitting device of claim 9, wherein the
organic material layer comprise at least one layer of a hole
blocking layer, an electron injection layer, and an electron
transport layer, and at least one layer of the hole blocking layer,
the electron injection layer, and the electron transport layer
comprises the hetero-cyclic compound.
11. The organic light emitting device of claim 9, wherein the
organic material layer comprises a light emitting layer, and the
light emitting layer comprises the hetero-cyclic compound.
12. The organic light emitting device of claim 9, wherein the
organic material layer comprises one or more layers of a hole
injection layer, a hole transport layer, and a layer which injects
and transports holes simultaneously, and one layer of the layers
comprises the hetero-cyclic compound.
13. The organic light emitting device of claim 9, wherein the
organic material layer comprising the hetero-cyclic compound
further comprises a compound represented by the following Chemical
Formula 2: ##STR00360## in Chemical Formula 2, R1' to R4' are the
same as or different from each other, and each independently
selected from the group consisting of hydrogen; deuterium; a
halogen group; --CN; a substituted or unsubstituted C.sub.1 to
C.sub.60 alkyl group; a substituted or unsubstituted C.sub.2 to
C.sub.60 alkenyl group; a substituted or unsubstituted C.sub.2 to
C.sub.60 alkynyl group; a substituted or unsubstituted C.sub.1 to
C.sub.60 alkoxy group; a substituted or unsubstituted C.sub.3 to
C.sub.60 cycloalkyl group; a substituted or unsubstituted C.sub.2
to C.sub.60 heterocycloalkyl group; a substituted or unsubstituted
C.sub.6 to C.sub.60 aryl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 heteroaryl group; --SiRR'R''; --P(.dbd.O)RR';
and an amine group which is unsubstituted or substituted with a
C.sub.1 to C.sub.20 alkyl group, a substituted or unsubstituted
C.sub.6 to C.sub.60 aryl group, or a C.sub.2 to C.sub.60 heteroaryl
group, or two or more adjacent groups combine with each other to
form a substituted or unsubstituted aliphatic or aromatic
hydrocarbon ring, L1' is a direct bond or a substituted or
unsubstituted C.sub.6 to C.sub.60 arylene group, Ar1' is a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; or a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group
including at least one of S and O, Ar2' is a substituted or
unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted or
unsubstituted C.sub.2 to C.sub.60 heteroaryl group, R, R', and R''
are the same as or different from each other, and each
independently hydrogen; deuterium; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted
or unsubstituted C.sub.2 to C.sub.60 heteroaryl group, and m', p'
and q' are each independently an integer of 0 to 4, and n' is an
integer of 0 to 2.
14. The organic light emitting device of claim 13, wherein Chemical
Formula 2 is represented by any one of the following Chemical
Formulae 11 to 22: ##STR00361## ##STR00362## in Chemical Formulae
11 to 22, the definitions of L1, Ar1, Ar2, R1 to R4, m, n, p, and q
are the same as those in Chemical Formula 2.
15. The organic light emitting device of claim 13, wherein Chemical
Formula 2 is represented by any one of the following compounds:
##STR00363## ##STR00364## ##STR00365## ##STR00366## ##STR00367##
##STR00368## ##STR00369## ##STR00370## ##STR00371## ##STR00372##
##STR00373## ##STR00374## ##STR00375## ##STR00376## ##STR00377##
##STR00378## ##STR00379## ##STR00380## ##STR00381## ##STR00382##
##STR00383## ##STR00384## ##STR00385## ##STR00386## ##STR00387##
##STR00388## ##STR00389## ##STR00390## ##STR00391## ##STR00392##
##STR00393## ##STR00394## ##STR00395## ##STR00396## ##STR00397##
##STR00398## ##STR00399## ##STR00400##
16. A composition for an organic material layer of an organic light
emitting device, comprising: both a hetero-cyclic compound
represented by the following Chemical Formula 1 and a compound
represented by the following Chemical Formula 2: ##STR00401## in
Chemical Formulae 1 and 2, L1 and L2 are the same as or different
from each other, and each independently a direct bond or a
substituted or unsubstituted C.sub.6 to C.sub.60 arylene group, Ar1
is a substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl
group comprising at least one N, Ar2 is represented by any one of
the following Chemical Formulae 3 and 4, ##STR00402## Y1 to Y4 are
the same as or different from each other, and each independently a
substituted or unsubstituted C.sub.6 to C.sub.60 aromatic
hydrocarbon ring; or a substituted or unsubstituted C.sub.2 to
C.sub.60 aromatic hetero ring, R1 to R7 and R1' to R4' are the same
as or different from each other, and each independently selected
from the group consisting of hydrogen; deuterium; a halogen group;
--CN; a substituted or unsubstituted C.sub.1 to C.sub.60 alkyl
group; a substituted or unsubstituted C.sub.2 to C.sub.60 alkenyl
group; a substituted or unsubstituted C.sub.2 to C.sub.60 alkynyl
group; a substituted or unsubstituted C.sub.1 to C.sub.60 alkoxy
group; a substituted or unsubstituted C.sub.3 to C.sub.60
cycloalkyl group; a substituted or unsubstituted C.sub.2 to
C.sub.60 heterocycloalkyl group; a substituted or unsubstituted
C.sub.6 to C.sub.60 aryl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 heteroaryl group; --SiRR'R''; --P(.dbd.O)RR';
and an amine group which is unsubstituted or substituted with a
C.sub.1 to C.sub.20 alkyl group, a substituted or unsubstituted
C.sub.6 to C.sub.60 aryl group, or a C.sub.2 to C.sub.60 heteroaryl
group, or two or more adjacent groups combine with each other to
form a substituted or unsubstituted aliphatic or aromatic
hydrocarbon ring, L1' is a direct bond or a substituted or
unsubstituted C.sub.6 to C.sub.60 arylene group, Ar1' is a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; or a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group
including at least one of S and O, Ar2' is a substituted or
unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted or
unsubstituted C.sub.2 to C.sub.60 heteroaryl group, R, R', and R''
are the same as or different from each other, and each
independently hydrogen; deuterium; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted
or unsubstituted C.sub.2 to C.sub.60 heteroaryl group, m', p' and
q' are each independently an integer of 0 to 4, and n' is an
integer of 0 to 2.
17. The composition for the organic material layer of the organic
light emitting device of claim 16, wherein a weight ratio of the
hetero-cyclic compound represented by Chemical Formula 1:the
compound represented by Chemical Formula 2 in the composition is
1:10 to 10:1.
Description
TECHNICAL FIELD
This application claims priority to and the benefit of Korean
Patent Application Nos. 10-2015-0106063, 10-2016-0057665, and
10-2016-0059084 filed in the Korean Intellectual Property Office on
Jul. 27, 2015, May 11, 2016, and May 13, 2016, respectively, the
entire contents of which are incorporated herein by reference.
The present application relates to a hetero-cyclic compound and an
organic light emitting device using the same.
BACKGROUND ART
An electroluminescence device is a kind of self-emitting type
display device, and has an advantage in that the viewing angle is
wide, the contrast is excellent, and the response speed is
fast.
An organic light emitting device has a structure in which an
organic thin film is disposed between two electrodes. When a
voltage is applied to an organic light emitting device having the
structure, electrons and holes injected from the two electrodes
combine with each other in an organic thin film to make a pair, and
then, emit light while being extinguished. The organic thin film
may be composed of a single layer or multi layers, if
necessary.
A material for the organic thin film may have a light emitting
function, if necessary. For example, as the material for the
organic thin film, it is also possible to use a compound, which may
itself constitute a light emitting layer alone, or it is also
possible to use a compound, which may serve as a host or a dopant
of a host-dopant-based light emitting layer. In addition, as a
material for the organic thin film, it is also possible to use a
compound, which may perform a function such as hole injection, hole
transport, electron blocking, hole blocking, electron transport or
electron injection.
In order to improve the performance, lifetime, or efficiency of the
organic light emitting device, there is a continuous need for
developing a material for an organic thin film.
DISCLOSURE
Technical Problem
It is necessary to perform studies on an organic light emitting
device including a compound having a chemical structure, which may
satisfy conditions required for a material which is available for
the organic light emitting device, for example, appropriate energy
levels, electrochemical stability, thermal stability, and the like,
and may perform various functions required for the organic light
emitting device according to the substituent.
Technical Solution
An exemplary embodiment of the present application provides a
hetero-cyclic compound represented by the following Chemical
Formula 1:
##STR00001##
In Chemical Formula 1,
L1 and L2 are the same as or different from each other, and each
independently a direct bond or a substituted or unsubstituted
C.sub.6 to C.sub.60 arylene group,
Ar1 is a substituted or unsubstituted C.sub.2 to C.sub.60
heteroaryl group including at least one N.
Ar2 is represented by any one of the following Chemical Formulae 3
and 4,
##STR00002##
in Chemical Formulae 3 and 4,
Y1 to Y4 are the same as or different from each other, and each
independently a substituted or unsubstituted C.sub.6 to C.sub.60
aromatic hydrocarbon ring; or a substituted or unsubstituted
C.sub.2 to C.sub.60 aromatic hetero ring,
R1 to R7 are the same as or different from each other, and each
independently selected from the group consisting of hydrogen;
deuterium; a halogen group; --CN; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkenyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkynyl group; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkoxy group; a substituted or unsubstituted
C.sub.3 to C.sub.60 cycloalkyl group; a substituted or
unsubstituted C.sub.2 to C.sub.60 heterocycloalkyl group; a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group;
--SiRR'R''; --P(.dbd.O)RR'; and an amine group which is
unsubstituted or substituted with a C.sub.1 to C.sub.20 alkyl
group, a substituted or unsubstituted C.sub.6 to C.sub.60 aryl
group, or a C.sub.2 to C.sub.60 heteroaryl group, or two or more
adjacent groups combine with each other to form a substituted or
unsubstituted aliphatic or aromatic hydrocarbon ring, and
R, R', and R'' are the same as or different from each other, and
are each independently hydrogen; deuterium; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted
or unsubstituted C.sub.2 to C.sub.60 heteroaryl group.
Further, another exemplary embodiment of the present application
provides an organic light emitting device including a positive
electrode, a negative electrode, and one or more organic material
layers provided between the positive electrode and the negative
electrode, in which one or more layers of the organic material
layers include the hetero-cyclic compound represented by Chemical
Formula 1.
In addition, still another exemplary embodiment of the present
application provides a composition for an organic material layer of
an organic light emitting device, which includes both the
hetero-cyclic compound represented by Chemical Formula 1 and a
compound represented by the following Chemical Formula 2.
##STR00003##
In Chemical Formula 2,
R1' to R4' are the same as or different from each other, and each
independently selected from the group consisting of hydrogen;
deuterium; a halogen group; --CN; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkenyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkynyl group; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkoxy group; a substituted or unsubstituted
C.sub.3 to C.sub.60 cycloalkyl group; a substituted or
unsubstituted C.sub.2 to C.sub.60 heterocycloalkyl group; a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group;
--SiRR'R''; --P(.dbd.O)RR'; and an amine group which is
unsubstituted or substituted with a C.sub.1 to C.sub.20 alkyl
group, a substituted or unsubstituted C.sub.6 to C.sub.60 aryl
group, or a C.sub.2 to C.sub.60 heteroaryl group, or two or more
adjacent groups combine with each other to form a substituted or
unsubstituted aliphatic or aromatic hydrocarbon ring,
L1' is a direct bond or a substituted or unsubstituted C.sub.6 to
C.sub.60 arylene group,
Ar1' is a substituted or unsubstituted C.sub.6 to C.sub.60 aryl
group; or a substituted or unsubstituted C.sub.2 to C.sub.60
heteroaryl group including at least one of S and O,
Ar2' is a substituted or unsubstituted C.sub.6 to C.sub.60 aryl
group; or a substituted or unsubstituted C.sub.2 to C.sub.60
heteroaryl group,
R, R', and R'' are the same as or different from each other, and
each independently hydrogen; deuterium; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted
or unsubstituted C.sub.2 to C.sub.60 heteroaryl group,
m', p' and q' are each independently an integer of 0 to 4, and
n' is an integer of 0 to 2.
Advantageous Effects
A hetero-cyclic compound according to an exemplary embodiment of
the present application may be used as a material for an organic
material layer of an organic light emitting device. The
hetero-cyclic compound may be used as a material for a hole
injection layer, a hole transport layer, a light emitting layer, an
electron transport layer, an electron injection layer, a charge
generation layer, and the like in an organic light emitting device.
In particular, the hetero-cyclic compound represented by Chemical
Formula 1 may be used as a material for an electron transport
layer, a hole transport layer, or a light emitting layer of the
organic light emitting device. In addition, when the hetero-cyclic
compound represented by Chemical Formula 1 is used for the organic
light emitting device, the driving voltage of the device may be
lowered, the light efficiency of the device may be improved, and
the lifetime characteristics of the device may be improved by the
thermal stability of the compound.
Furthermore, the hetero-cyclic compound represented by Chemical
Formula 1 and the compound represented by chemical Formula 2 may be
used simultaneously as a material for a light emitting layer of an
organic light emitting device. In addition, when the hetero-cyclic
compound represented by Chemical Formula 1 and the hetero-cyclic
compound represented by Chemical Formula 2 are simultaneously used
for the organic light emitting device, the driving voltage of the
device may be lowered, the light efficiency of the device may be
improved, and the lifetime characteristics of the device may be
improved by the thermal stability of the compound.
DESCRIPTION OF DRAWINGS
FIGS. 1 to 3 each are views schematically illustrating a stacking
structure of an organic light emitting device according to an
exemplary embodiment of the present application.
FIG. 4 illustrates a measurement graph of LTPL of Compound 1-2 at a
wavelength of 363 nm.
FIG. 5 illustrates a measurement graph of PL of Compound 1-2 at a
wavelength of 238 nm.
FIG. 6 illustrates a UV absorption spectrum of Compound 1-2.
FIG. 7 illustrates a measurement graph of LTPL of Compound 1-11 at
a wavelength of 339 nm.
FIG. 8 illustrates a measurement graph of PL of Compound 1-11 at a
wavelength of 234 nm.
FIG. 9 illustrates a UV absorption spectrum of Compound 1-11.
FIG. 10 illustrates a measurement graph of LTPL of Compound 1-23 at
a wavelength of 241 nm.
FIG. 11 illustrates a measurement graph of PL of Compound 1-23 at a
wavelength of 241 nm.
FIG. 12 illustrates a UV absorption spectrum of Compound 1-23.
FIG. 13 illustrates a measurement graph of LTPL of Compound 1-27 at
a wavelength of 340 nm.
FIG. 14 illustrates a measurement graph of PL of Compound 1-27 at a
wavelength of 241 nm.
FIG. 15 illustrates a UV absorption spectrum of Compound 1-27.
FIG. 16 illustrates a measurement graph of LTPL of Compound 1-33 at
a wavelength of 291 nm.
FIG. 17 illustrates a measurement graph of PL of Compound 1-33 at a
wavelength of 239 nm.
FIG. 18 illustrates a UV absorption spectrum of Compound 1-33.
FIG. 19 illustrates a measurement graph of LTPL of Compound 1-39 at
a wavelength of 259 nm.
FIG. 20 illustrates a measurement graph of PL of Compound 1-39 at a
wavelength of 259 nm.
FIG. 21 illustrates a UV absorption spectrum of Compound 1-39.
FIG. 22 illustrates a measurement graph of LTPL of Compound 1-41 at
a wavelength of 260 nm.
FIG. 23 illustrates a measurement graph of PL of Compound 1-41 at a
wavelength of 260 nm.
FIG. 24 illustrates a UV absorption spectrum of Compound 1-41.
FIG. 25 illustrates a measurement graph of LTPL of Compound 1-65 at
a wavelength of 361 nm.
FIG. 26 illustrates a measurement graph of PL of Compound 1-65 at a
wavelength of 235 nm.
FIG. 27 illustrates a UV absorption spectrum of Compound 1-65.
FIG. 28 illustrates a measurement graph of LTPL of Compound 1-66 at
a wavelength of 360 nm.
FIG. 29 illustrates a measurement graph of PL of Compound 1-66 at a
wavelength of 307 nm.
FIG. 30 illustrates a UV absorption spectrum of Compound 1-66.
FIG. 31 illustrates a measurement graph of LTPL of Compound 1-67 at
a wavelength of 361 nm.
FIG. 32 illustrates a measurement graph of PL of Compound 1-67 at a
wavelength of 266 nm.
FIG. 33 illustrates a UV absorption spectrum of Compound 1-67.
FIG. 34 illustrates a measurement graph of LTPL of Compound 1-69 at
a wavelength of 344 nm.
FIG. 35 illustrates a measurement graph of PL of Compound 1-69 at a
wavelength of 308 nm.
FIG. 36 illustrates a UV absorption spectrum of Compound 1-69.
FIG. 37 illustrates a measurement graph of LTPL of Compound 1-70 at
a wavelength of 344 nm.
FIG. 38 illustrates a measurement graph of PL of Compound 1-70 at a
wavelength of 267 nm.
FIG. 39 illustrates a UV absorption spectrum of Compound 1-70.
FIG. 40 illustrates a measurement graph of LTPL of Compound 1-71 at
a wavelength of 344 nm.
FIG. 41 illustrates a measurement graph of PL of Compound 1-71 at a
wavelength of 241 nm.
FIG. 42 illustrates a UV absorption spectrum of Compound 1-71.
FIG. 43 illustrates a measurement graph of LTPL of Compound 1-78 at
a wavelength of 361 nm.
FIG. 44 illustrates a measurement graph of PL of Compound 1-78 at a
wavelength of 263 nm.
FIG. 45 illustrates a UV absorption spectrum of Compound 1-78.
FIG. 46 illustrates a measurement graph of LTPL of Compound 1-82 at
a wavelength of 344 nm.
FIG. 47 illustrates a measurement graph of PL of Compound 1-82 at a
wavelength of 307 nm.
FIG. 48 illustrates a UV absorption spectrum of Compound 1-82.
FIG. 49 illustrates a measurement graph of LTPL of Compound 1-84 at
a wavelength of 363 nm.
FIG. 50 illustrates a measurement graph of PL of Compound 1-84 at a
wavelength of 298 nm.
FIG. 51 illustrates a UV absorption spectrum of Compound 1-84.
FIG. 52 illustrates a measurement graph of LTPL of Compound 1-99 at
a wavelength of 355 nm.
FIG. 53 illustrates a measurement graph of PL of Compound 1-99 at a
wavelength of 355 nm.
FIG. 54 illustrates a UV absorption spectrum of Compound 1-99.
EXPLANATION OF REFERENCE NUMERALS AND SYMBOLS
100: Substrate 200: Positive electrode 300: Organic material layer
301: Hole injection layer 302: Hole transport layer 303: Light
emitting layer 304: Hole blocking layer 305: Electron transport
layer 306: Electron injection layer 400: Negative electrode
BEST MODE
Hereinafter, the present application will be described in
detail.
A hetero-cyclic compound according to an exemplary embodiment of
the present application is represented by Chemical Formula 1. More
specifically, the hetero-cyclic compound represented by Chemical
Formula 1 may be used as a material for an organic material layer
of an organic light emitting device by the structural
characteristics of the core structure and the substituent as
described above.
In Chemical Formulae 3 and 4, * denotes a position to be linked to
L2 of Chemical Formula 1.
According to an exemplary embodiment of the present application,
Chemical Formula 3 may be represented by any one of the following
Chemical Formulae.
##STR00004##
In the structural formulae, X1 to X6 are the same as or different
from each other, and each independently NR, S, O, or CR'R'',
R8 to R14 are the same as or different from each other, and each
independently selected from the group consisting of hydrogen;
deuterium; a halogen group; --CN; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkenyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkynyl group; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkoxy group; a substituted or unsubstituted
C.sub.3 to C.sub.60 cycloalkyl group; a substituted or
unsubstituted C.sub.2 to C.sub.60 heterocycloalkyl group; a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group;
--SiRR'R''; --P(.dbd.O)RR'; and an amine group which is
unsubstituted or substituted with a C.sub.1 to C.sub.20 alkyl
group, a substituted or unsubstituted C.sub.6 to C.sub.60 aryl
group, or a C.sub.2 to C.sub.60 heteroaryl group, or two or more
adjacent groups combine with each other to form a substituted or
unsubstituted aliphatic or aromatic hydrocarbon ring,
R, R', and R'' are the same as or different from each other, and
each independently hydrogen; deuterium; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted
or unsubstituted C.sub.2 to C.sub.60 heteroaryl group, and
m is an integer of 0 to 8, and n, o, p, q, r, and s are each
independently an integer of 0 to 6.
According to an exemplary embodiment of the present application,
Chemical Formula 4 may be represented by any one of the following
Chemical Formulae.
##STR00005##
In the structural formulae, X7 and X8 are the same as or different
from each other, and each independently NR, S, O, or CR'R'',
R15 to R18 are the same as or different from each other, and each
independently selected from the group consisting of hydrogen;
deuterium; a halogen group; --CN; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkenyl group; a substituted or unsubstituted
C.sub.2 to C.sub.60 alkynyl group; a substituted or unsubstituted
C.sub.1 to C.sub.60 alkoxy group; a substituted or unsubstituted
C.sub.3 to C.sub.60 cycloalkyl group; a substituted or
unsubstituted C.sub.2 to C.sub.60 heterocycloalkyl group; a
substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; a
substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group;
--SiRR'R''; --P(.dbd.O)RR'; and an amine group which is
unsubstituted or substituted with a C.sub.1 to C.sub.20 alkyl
group, a substituted or unsubstituted C.sub.6 to C.sub.60 aryl
group, or a C.sub.2 to C.sub.60 heteroaryl group, or two or more
adjacent groups combine with each other to form a substituted or
unsubstituted aliphatic or aromatic hydrocarbon ring,
R, R', and R'' are the same as or different from each other, and
each independently hydrogen; deuterium; --CN; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or
unsubstituted C.sub.3 to C.sub.60 cycloalkyl group; a substituted
or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted
or unsubstituted C.sub.2 to C.sub.60 heteroaryl group, and
t is an integer of 0 to 7.
According to an exemplary embodiment of the present specification,
Chemical Formula 1 may be represented by any one of the following
Chemical Formulae 5 to 10.
##STR00006## ##STR00007##
In Chemical Formulae 5 to 10, the definitions of R1 to R6, R8, R9,
R12, R13, R16, L1, Ar1, X1, X4, X5, m, n, q, r, and t are the same
as those in Chemical Formula 1 and the structural formulae.
In an exemplary embodiment of the present application, R1 to R6 of
Chemical Formula 1 may be each independently hydrogen or
deuterium.
In an exemplary embodiment of the present application, R8 to R18
may be each independently hydrogen; deuterium; a substituted or
unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted or
unsubstituted C.sub.2 to C.sub.60 heteroaryl group.
In an exemplary embodiment of the present application, R, R', and
R'' of Chemical Formula 1 are the same as or different from each
other, and each independently hydrogen; a substituted or
unsubstituted C.sub.1 to C.sub.60 alkyl group; or a substituted or
unsubstituted C.sub.6 to C.sub.60 aryl group.
Further, the composition for an organic material layer of an
organic light emitting device according to an exemplary embodiment
of the present application may include both the hetero-cyclic
compound represented by Chemical Formula 1 and the compound
represented by Chemical Formula 2.
According to an exemplary embodiment of the present application,
Chemical Formula 2 may be represented by any one of the following
Chemical Formulae 11 to 22.
##STR00008## ##STR00009## ##STR00010## ##STR00011##
In Chemical Formulae 11 to 22, the definitions of L1, Ar1, Ar2, R1
to R4, m, n, p, and q are the same as those in Chemical Formula
2.
In an exemplary embodiment of the present application, when m', n',
p', and q' of Chemical Formula 2 are each independently 2 or more,
two or more R1' to R4' may be each the same as or different from
each other.
In an exemplary embodiment of the present application, R1' to R4'
of Chemical Formula 2 may be each independently hydrogen or
deuterium.
In an exemplary embodiment of the present application, Ar1' of
Chemical Formula 2 may be a substituted or unsubstituted C.sub.6 to
C.sub.60 aryl group; a substituted or unsubstituted C.sub.2 to
C.sub.60 heteroaryl group including S; or a substituted or
unsubstituted C.sub.2 to C.sub.60 heteroaryl group including O.
In an exemplary embodiment of the present application, Ar1' of
Chemical Formula 2 may be a phenyl group, a biphenyl group, a
naphthyl group, a fluorene group in which an alkyl group is
substituted, a dibenzothiophene group, or a dibenzofuran group.
In an exemplary embodiment of the present application, Ar2' of
Chemical Formula 2 may be a substituted or unsubstituted C.sub.6 to
C.sub.60 aryl group.
In an exemplary embodiment of the present application, Ar2' of
Chemical Formula 2 may be a phenyl group.
In the present application, the substituents of Chemical Formulae 1
and 2 will be more specifically described as follows.
In the present specification, "substituted or unsubstituted" means
being unsubstituted or substituted with one or more substituents
selected from the group consisting of deuterium; a halogen group;
--CN; a C.sub.1 to C.sub.60 alkyl group; a C.sub.2 to C.sub.60
alkenyl group; a C.sub.2 to C.sub.60 alkynyl group; a C.sub.3 to
C.sub.60 cycloalkyl group; a C.sub.2 to C.sub.60 heterocycloalkyl
group; a C.sub.6 to C.sub.60 aryl group; a C.sub.2 to C.sub.60
heteroaryl group; --SiRR'R''; --P(.dbd.O)RR'; a C.sub.1 to C.sub.20
alkylamine group; a C.sub.6 to C.sub.60 arylamine group; and a
C.sub.2 to C.sub.60 heteroarylamine group, being unsubstituted or
substituted with a substituent to which two or more substituents
among the substituents are linked, or being unsubstituted or
substituted with a substituent to which two or more substituents
selected among the substituents are linked. For example, "the
substituent to which two or more substituents are linked" may be a
biphenyl group. That is, the biphenyl group may also be an aryl
group, and may be interpreted as a substituent to which two phenyl
groups are linked. The additional substituents may also be
additionally substituted. R, R', and R'' are the same as or
different from each other, and each independently hydrogen;
deuterium; --CN; a substituted or unsubstituted C.sub.1 to C.sub.60
alkyl group; a substituted or unsubstituted C.sub.3 to C.sub.60
cycloalkyl group; a substituted or unsubstituted C.sub.6 to
C.sub.60 aryl group; or a substituted or unsubstituted C.sub.2 to
C.sub.60 heteroaryl group.
According to an exemplary embodiment of the present specification,
the "substituted or unsubstituted" is unsubstituted or substituted
with one or more substituents selected from the group consisting of
deuterium, a halogen group, --CN, SiRR'R'', P(.dbd.O)RR', a C.sub.1
to C.sub.20 straight-chained or branch-chained alkyl group, a
C.sub.6 to C.sub.60 aryl group, and a C.sub.2 to C.sub.60
heteroaryl group, and
R, R', and R'' are the same as or different from each other, and
each independently hydrogen; deuterium; --CN; a C.sub.1 to C.sub.60
alkyl group which is unsubstituted or substituted with deuterium, a
halogen group, --CN, a C.sub.1 to C.sub.20 alkyl group, a C.sub.6
to C.sub.60 aryl group, and a C.sub.2 to C.sub.60 heteroaryl group;
a C.sub.3 to C.sub.60 cycloalkyl group which is unsubstituted or
substituted with deuterium, halogen, --CN, a C.sub.1 to C.sub.20
alkyl group, a C.sub.6 to C.sub.60 aryl group, and a C.sub.2 to
C.sub.60 heteroaryl group; a C.sub.6 to C.sub.60 aryl group which
is unsubstituted or substituted with deuterium, halogen, --CN, a
C.sub.1 to C.sub.20 alkyl group, a C.sub.6 to C.sub.60 aryl group,
and a C.sub.2 to C.sub.60 heteroaryl group; or a C.sub.2 to
C.sub.60 heteroaryl group which is unsubstituted or substituted
with deuterium, halogen, --CN, a C.sub.1 to C.sub.20 alkyl group, a
C.sub.6 to C.sub.60 aryl group, and a C.sub.2 to C.sub.60
heteroaryl group.
The term "substitution" means that a hydrogen atom bonded to a
carbon atom of a compound is changed into another substituent, and
a position to be substituted is not limited as long as the position
is a position at which the hydrogen atom is substituted, that is, a
position at which the substituent may be substituted, and when two
or more are substituted, the two or more substituents may be the
same as or different from each other.
In the present specification, the halogen may be fluorine,
chlorine, bromine or iodine.
In the present specification, the alkyl group includes a
straight-chain or branched-chain having 1 to 60 carbon atoms, and
may be additionally substituted with another substituent. The
number of carbon atoms of the alkyl group may be 1 to 60,
specifically 1 to 40, and more specifically 1 to 20. Specific
examples thereof include a methyl group, an ethyl group, a propyl
group, an n-propyl group, an isopropyl group, a butyl group, an
n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl
group, a 1-methyl-butyl group, a 1-ethyl-butyl group, a pentyl
group, an n-pentyl group, an isopentyl group, a neopentyl group, a
tert-pentyl group, a hexyl group, an n-hexyl group, a
1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl
group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl
group, an n-heptyl group, a 1-methylhexyl group, a
cyclopentylmethyl group, a cyclohexylmethyl group, an octyl group,
an n-octyl group, a tert-octyl group, a 1-methylheptyl group, a
2-ethylhexyl group, a 2-propylpentyl group, an n-nonyl group, a
2,2-dimethylheptyl group, a 1-ethyl-propyl group, a
1,1-dimethyl-propyl group, an isohexyl group, a 2-methylpentyl
group, a 4-methylhexyl group, a 5-methylhexyl group, and the like,
but are not limited thereto.
In the present specification, the alkenyl group includes a
straight-chain or branched-chain having 2 to 60 carbon atoms, and
may be additionally substituted with another substituent. The
number of carbon atoms of the alkenyl group may be 2 to 60,
specifically 2 to 40, and more specifically 2 to 20. Specific
examples thereof include a vinyl group, a 1-propenyl group, an
isopropenyl group, a 1-butenyl group, a 2-butenyl group, a
3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a
3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl
group, an allyl group, a 1-phenylvinyl-1-yl group, a
2-phenylvinyl-1-yl group, a 2,2-diphenylvinyl-1-yl group, a
2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, a
2,2-bis(diphenyl-1-yl)vinyl-1-yl group, a stilbenyl group, a
styrenyl group, and the like, but are not limited thereto.
In the present specification, the alkynyl group includes a
straight-chain or branched-chain having 2 to 60 carbon atoms, and
may be additionally substituted with another substituent. The
number of carbon atoms of the alkynyl group may be 2 to 60,
specifically 2 to 40, and more specifically 2 to 20.
In the present specification, the cycloalkyl group includes a
monocycle or polycycle having 3 to 60 carbon atoms, and may be
additionally substituted with another substituent. Here, the
polycycle means a group in which a cycloalkyl group is directly
linked to or fused with another cyclic group. Here, another cyclic
group may also be a cycloalkyl group, but may also be another kind
of cyclic group, for example, a heterocycloalkyl group, an aryl
group, a heteroaryl group, and the like. The number of carbon atoms
of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and
more specifically 5 to 20. Specific examples thereof include a
cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a
3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a
cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl
group, a 2,3-dimethylcyclohexyl group, a 3,4,5-trimethylcyclohexyl
group, a 4-tert-butylcyclohexyl group, a cycloheptyl group, a
cyclooctyl group, and the like, but are not limited thereto.
In the present specification, the heterocycloalkyl group includes
O, S, Se, N, or Si as a heteroatom, includes a monocycle or
polycycle having 2 to 60 carbon atoms, and may be additionally
substituted with another substituent. Here, the polycycle means a
group in which a heterocycloalkyl group is directly linked to or
fused with another cyclic group. Here, another cyclic group may
also be a heterocycloalkyl group, but may also be another kind of
cyclic group, for example, a cycloalkyl group, an aryl group, a
heteroaryl group, and the like. The number of carbon atoms of the
heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and
more specifically 3 to 20.
In the present specification, the aryl group includes a monocycle
or polycycle having 6 to 60 carbon atoms, and may be additionally
substituted with another substituent. Here, the polycycle means a
group in which an aryl group is directly linked to or fused with
another cyclic group. Here, another cyclic group may also be an
aryl group, but may also be another kind of cyclic group, for
example, a cycloalkyl group, a heterocycloalkyl group, a heteroaryl
group, and the like. The aryl group includes a spiro group. The
number of carbon atoms of the aryl group may be 6 to 60,
specifically 6 to 40, and more specifically 6 to 25. Specific
examples of the aryl group include a phenyl group, a biphenyl
group, a triphenyl group, a naphthyl group, an anthryl group, a
chrysenyl group, a phenanthrenyl group, a perylenyl group, a
fluoranthenyl group, a triphenylenyl group, a phenalenyl group, a
pyrenyl group, a tetracenyl group, a pentacenyl group, a fluorenyl
group, an indenyl group, an acenaphthylenyl group, a benzofluorenyl
group, a spirobifluorenyl group, a 2,3-dihydro-1H-indenyl group, a
fused cyclic group thereof, and the like, but are not limited
thereto.
In the present specification, the spiro group is a group including
a spiro structure, and may have 15 to 60 carbon atoms. For example,
the spiro group may include a structure in which a
2,3-dihydro-1H-indene group or a cyclohexane group is spiro-bonded
to a fluorenyl group. Specifically, the following spiro group may
include any one of the groups of the following structural
formulae.
##STR00012##
In the present specification, the heteroaryl group includes S, O,
Se, N, or Si as a heteroatom, includes a monocycle or polycycle
having 2 to 60 carbon atoms, and may be additionally substituted
with another substituent. Here, the polycycle means a group in
which a heteroaryl group is directly linked to or fused with
another cyclic group. Here, another cyclic group may also be a
heteroaryl group, but may also be another kind of cyclic group, for
example, a cycloalkyl group, a heterocycloalkyl group, an aryl
group, and the like. The number of carbon atoms of the heteroaryl
group may be 2 to 60, specifically 2 to 40, and more specifically 3
to 25. Specific examples of the heteroaryl group include a pyridyl
group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a
furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl
group, an oxazolyl group, an isoxazolyl group, a thiazolyl group,
an isothiazolyl group, a triazolyl group, a furazanyl group, an
oxadiazolyl group, a thiadiazolyl group, a dithiazolyl group, a
tetrazolyl group, a pyranyl group, a thiopyranyl group, a diazinyl
group, an oxazinyl group, a thiazinyl group, a dioxinyl group, a
triazinyl group, a tetrazinyl group, a quinolyl group, an
isoquinolyl group, a quinazolinyl group, an isoquinazolinyl group,
a quinozolilyl group, a naphthyridyl group, an acridinyl group, a
phenanthridinyl group, an imidazopyridinyl group, a diaza
naphthalenyl group, a triazaindene group, an indolyl group, an
indolizinyl group, a benzothiazolyl group, a benzoxazolyl group, a
benzimidazolyl group, a benzothiophene group, a benzofuran group, a
dibenzothiophene group, a dibenzofuran group, a carbazolyl group, a
benzocarbazolyl group, a dibenzocarbazolyl group, a phenazinyl
group, a dibenzosilole group, spirobi (dibenzosilole), a
dihydrophenazinyl group, a phenoxazinyl group, a phenanthridyl
group, an imidazopyridinyl group, a thienyl group, an
indolo[2,3-a]carbazolyl group, an indolo[2,3-b]carbazolyl group, an
indolinyl group, a 10,11-dihydro-dibenzo[b,f]azepin group, a
9,10-dihydroacridinyl group, a phenanthrazinyl group, a
phenothiazinyl group, a phthalazinyl group, a naphthylidinyl group,
a phenanthrolinyl group, a benzo[c][1,2,]thiadiazolyl group, a
5,10-dihydrodibenzo[b,e][1,4]azasilinyl, a
pyrazolo[1,5-c]quinazolinyl group, a pyrido[1,2-b]indazolyl group,
a pyrido[1,2-a]imidazo[1,2-e]indolinyl group, a
5,11-dihydroindeno[1,2-b]carbazolyl group, and the like, but are
not limited thereto.
In the present specification, the amine group may be selected from
the group consisting of a monoalkylamine group; a monoarylamine
group; a monoheteroarylamine group; --NH.sub.2; a dialkylamine
group; a diarylamine group; a diheteroarylamine group; an
alkylarylamine group; an alkylheteroarylamine group; and an
arylheteroarylamine group, and the number of carbon atoms thereof
is not particularly limited, but is preferably 1 to 30. Specific
examples of the amine group include a methylamine group, a
dimethylamine group, an ethylamine group, a diethylamine group, a
phenylamine group, a naphthylamine group, a biphenylamine group, a
dibiphenylamine group, an anthracenylamine group, a
9-methyl-anthracenylamine group, a diphenylamine group, a
phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine
group, a triphenylamine group, a biphenylnaphthylamine group, a
phenylbiphenylamine group, a biphenylfluorenylamine group, a
phenyltriphenylenylamine group, a biphenyltriphenylenylamine group,
and the like, but are not limited thereto.
In the present specification, the arylene group means that there
are two bonding positions in an aryl group, that is, a divalent
group. The above-described description on the aryl group may be
applied, except that the arylene groups are each a divalent group.
Further, the heteroarylene group means that there are two bonding
positions in a heteroaryl group, that is, a divalent group. The
above-described description on the heteroaryl group may be applied,
except that these are each a divalent group.
According to an exemplary embodiment of the present application,
Chemical Formula 1 may be represented by any one of the following
compounds, but is not limited thereto.
##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017##
##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022##
##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027##
##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032##
##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037##
##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042##
##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047##
##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052##
##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057##
##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062##
##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067##
##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072##
##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077##
##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082##
##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087##
##STR00088##
According to an exemplary embodiment of the present application,
Chemical Formula 2 may be represented by any one of the following
compounds, but is not limited thereto.
##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093##
##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098##
##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103##
##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108##
##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113##
##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118##
##STR00119##
Further, it is possible to synthesize a compound having inherent
characteristics of a substituent introduced by introducing various
substituents into the structures of Chemical Formulae 1 and 2. For
example, it is possible to synthesize a material which satisfies
conditions required for each organic material layer by introducing
a substituent usually used for a hole injection layer material, a
material for transporting holes, a light emitting layer material,
an electron transport layer material, and a charge generation layer
material, which are used for preparing an organic light emitting
device, into the core structure.
In addition, it is possible to finely adjust an energy band gap by
introducing various substituents into the structures of Chemical
Formulae 1 and 2, and meanwhile, it is possible to improve
characteristics at the interface between organic materials and
diversify the use of material.
Meanwhile, the hetero-cyclic compound has a high glass transition
temperature (Tg) and thus has excellent thermal stability. The
increase in thermal stability becomes an important factor which
provides driving stability to a device.
The hetero-cyclic compound according to an exemplary embodiment of
the present application may be prepared by a multi-step chemical
reaction. Some intermediate compounds are first prepared, and a
compound of Chemical Formula 1 or 2 may be prepared from the
intermediate compounds. More specifically, the hetero-cyclic
compound according to an exemplary embodiment of the present
application may be prepared based on the Preparation Examples to be
described below.
Furthermore, another exemplary embodiment of the present
application provides a composition for an organic material layer of
an organic light emitting device, which includes both the
hetero-cyclic compound represented by Chemical Formula 1 and the
compound represented by Chemical Formula 2.
The specific contents on the hetero-cyclic compound represented by
Chemical Formula 1 and the compound represented by Chemical Formula
2 are the same as those described above.
The weight ratio of the hetero-cyclic compound represented by
Chemical Formula 1:the compound represented by Chemical Formula 2
in the composition may be 1:10 to 10:1, 1:8 to 8:1, 1:5 to 5:1, and
1:2 to 2:1, but is not limited thereto.
The composition may be used when an organic material for an organic
light emitting device is formed, and particularly, may be more
preferably used when a host of a light emitting layer is
formed.
The composition is in a form in which two or more compounds are
simply mixed, materials in a powder state may also be mixed before
an organic material layer of an organic light emitting device is
formed, and it is possible to mix compounds in a liquid state at a
temperature which is equal to or more than a suitable temperature.
The composition is in a solid state at a temperature which is equal
to or less than the melting point of each material, and may be
maintained as a liquid if the temperature is adjusted.
Another exemplary embodiment of the present application provides an
organic light emitting device including the hetero-cyclic compound
represented by Chemical Formula 1.
Further, the organic light emitting device according to an
exemplary embodiment of the present application includes a positive
electrode, a negative electrode, and one or more organic material
layers provided between the positive electrode and the negative
electrode, in which one or more layers of the organic material
layers include the hetero-cyclic compound represented by Chemical
Formula 1 and the compound represented by Chemical Formula 2.
The organic light emitting device according to an exemplary
embodiment of the present application may be manufactured by
typical methods and materials for manufacturing an organic light
emitting device, except that the one or more organic material
layers are formed by using the hetero-cyclic compound represented
by Chemical Formula 1 and the hetero-cyclic compound represented by
Chemical Formula 2, which are described above.
The compound represented by Chemical Formula 1 and the
hetero-cyclic compound represented by Chemical Formula 2 may be
formed as an organic material layer by not only a vacuum deposition
method, but also a solution application method when an organic
light emitting device is manufactured. Here, the solution
application method means spin coating, dip coating, inkjet
printing, screen printing, a spray method, roll coating, and the
like, but is not limited thereto.
Specifically, the organic light emitting device according to an
exemplary embodiment of the present application includes a positive
electrode, a negative electrode, and one or more organic material
layers provided between the positive electrode and the negative
electrode, in which one or more of the organic material layers
include the hetero-cyclic compound represented by Chemical Formula
1.
Further, the organic light emitting device according to an
exemplary embodiment of the present application includes a positive
electrode, a negative electrode, and an one or more organic
material layers provided between the positive electrode and the
negative electrode, in which one or more layers of the organic
material layers include the hetero-cyclic compound represented by
Chemical Formula 1 and the hetero-cyclic compound represented by
Chemical Formula 2.
FIGS. 1 to 3 exemplify the stacking sequence of the electrodes and
the organic material layers of the organic light emitting device
according to an exemplary embodiment of the present application.
However, the scope of the present application is not intended to be
limited by these drawings, and the structure of the organic light
emitting device known in the art may also be applied to the present
application.
According to FIG. 1, an organic light emitting device in which a
positive electrode 200, an organic material layer 300, and a
negative electrode 400 are sequentially stacked on a substrate 100
is illustrated. However, the organic light emitting device is not
limited only to such a structure, and as in FIG. 2, an organic
light emitting device in which a negative electrode, an organic
material layer, and a positive electrode are sequentially stacked
on a substrate may also be implemented.
FIG. 3 exemplifies a case where an organic material layer is a
multilayer. An organic light emitting device according to FIG. 3
includes a hole injection layer 301, a hole transport layer 302, a
light emitting layer 303, a hole blocking layer 304, an electron
transport layer 305, and an electron injection layer 306. However,
the scope of the present application is not limited by the stacking
structure as described above, and if necessary, the other layers
except for the light emitting layer may be omitted, and another
necessary functional layer may be further added.
The organic light emitting device according to the present
specification may be manufactured by materials and methods known in
the art, except that one or more layers in the organic material
layers include the hetero-cyclic compound represented by Chemical
Formula 1, or include both the hetero-cyclic compound represented
by Chemical Formula 1 and the hetero-cyclic compound represented by
Chemical Formula 2.
The hetero-cyclic compound represented by Chemical Formula 1 may
alone constitute one or more layers of the organic material layers
of the organic light emitting device. However, the hetero-cyclic
compound represented by Chemical Formula 1 may be mixed with
another material, if necessary, to constitute an organic material
layer.
The hetero-cyclic compound represented by Chemical Formula 1 may be
used as a material for an electron transport layer, a hole blocking
layer, or a light emitting layer, and the like in the organic light
emitting device. As an example, the hetero-cyclic compound
represented by Chemical Formula 1 may be used as a material for an
electron transport layer, a hole transport layer, or a light
emitting layer of the organic light emitting device.
Furthermore, the hetero-cyclic compound represented by Chemical
Formula 1 may be used as a material for a light emitting layer in
the organic light emitting device. As an example, the hetero-cyclic
compound represented by Chemical Formula 1 may be used as a
material for a phosphorescent host of a light emitting layer in the
organic light emitting device.
Further, the organic material layer including the hetero-cyclic
compound represented by Chemical Formula 1 and the hetero-cyclic
compound represented by Chemical Formula 2 may additionally include
another material, if necessary.
The hetero-cyclic compound represented by Chemical Formula 1 and
the hetero-cyclic compound represented by chemical Formula 2 may be
used as a material for a charge generation layer in the organic
light emitting device.
The hetero-cyclic compound represented by Chemical Formula 1 and
the hetero-cyclic compound represented by chemical Formula 2 may be
used as a material for an electron transport layer, a hole blocking
layer, and a light emitting layer, and the like in the organic
light emitting device. As an example, the hetero-cyclic compound
represented by Chemical Formula 1 and the hetero-cyclic compound
represented by Chemical Formula 2 may be used as a material for an
electron transport layer, a hole transport layer, or a light
emitting layer of the organic light emitting device.
Furthermore, the hetero-cyclic compound represented by Chemical
Formula 1 and the compound represented by chemical Formula 2 may be
used as a material for a light emitting layer in the organic light
emitting device. As an example, the hetero-cyclic compound
represented by Chemical Formula 1 and the compound represented by
chemical Formula 2 may be used as a material for a phosphorescent
host of a light emitting layer in the organic light emitting
device.
In the organic light emitting device according to an exemplary
embodiment of the present application, materials other than the
hetero-cyclic compound of Chemical Formula 1 and the hetero-cyclic
compound of Chemical Formula 2 will be exemplified below, but these
materials are provided only for exemplification and are not for
limiting the scope of the present application, and may be replaced
with materials publicly known in the art.
As a material for the positive electrode, materials having a
relatively high work function may be used, and a transparent
conductive oxide, a metal or a conductive polymer, and the like may
be used. Specific examples of the positive electrode material
include: a metal, such as vanadium, chromium, copper, zinc, and
gold, or alloys thereof; a metal oxide, such as zinc oxide, indium
oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); a
combination of metal and oxide, such as ZnO:Al or SnO.sub.2:Sb; a
polymer, such as poly(3-methyl compound),
poly[3,4-(ethylene-1,2-dioxy)compound] (PEDT), polypyrrole, and
polyaniline, and the like, but are not limited thereto.
As a material for the negative electrode, materials having a
relatively low work function may be used, and a metal, a metal
oxide, or a conductive polymer, and the like may be used. Specific
examples of the negative electrode material include: a metal, such
as magnesium, calcium, sodium, potassium, titanium, indium,
yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or
alloys thereof; a multi-layered structural material, such as LiF/Al
or LiO.sub.2/Al, and the like, but are not limited thereto.
As a hole injection material, a publicly-known hole injection
material may also be used, and it is possible to use, for example,
a phthalocyanine compound such as copper phthalocyanine disclosed
in U.S. Pat. No. 4,356,429 or starburst-type amine derivatives
described in the document [Advanced Material, 6, p. 677 (1994)],
for example, tris(4-carbazoyl-9-ylphenyl)amine (TCTA),
4,4',4''-tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA),
1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB),
polyaniline/dodecylbenzenesulfonic acid or
poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate), which is
a soluble conductive polymer, polyaniline/camphor sulfonic acid or
polyaniline/poly(4-styrene-sulfonate), and the like.
As the hole transport material, a pyrazoline derivative, an
arylamine-based derivative, a stilbene derivative, a
triphenyldiamine derivative, and the like may be used, and a
low-molecular weight or polymer material may also be used.
As the electron transport material, it is possible to use an
oxadiazole derivative, anthraquinodimethane and a derivative
thereof, benzoquinone and a derivative thereof, naphthoquinone and
a derivative thereof, anthraquinone and a derivative thereof,
tetracyanoanthraquinodimethane and a derivative thereof, a
fluorenone derivative, diphenyldicyanoethylene and a derivative
thereof, a diphenoquinone derivative, a metal complex of
8-hydroxyquinoline and a derivative thereof, and the like, and a
low-molecular weight material and a polymer material may also be
used.
As the electron injection material, for example, LiF is
representatively used in the art, but the present application is
not limited thereto.
As the light emitting material, a red, green, or blue light
emitting material may be used, and if necessary, two or more light
emitting materials may be mixed and used. In this case, two or more
light emitting materials are deposited or used as an individual
supply source, or pre-mixed to be deposited and used as one supply
source. Further, as the light emitting material, a fluorescent
material may also be used, but a phosphorescent material may also
be used. As the light emitting material, it is also possible to use
alone a material which emits light by combining holes and electrons
each injected from the positive electrode and the negative
electrode, but materials in which a host material and a dopant
material work together to emit light may also be used.
When hosts of the light emitting material are mixed and used, the
same series hosts may also be mixed and used, and different series
hosts may also be mixed and used. For example, two or more
materials selected from n-type host materials or p-type host
materials may be used as a host material for a light emitting
layer.
The organic light emitting device according to an exemplary
embodiment of the present application may be a top emission type, a
bottom emission type, or a dual emission type according to the
material to be used.
The hetero-cyclic compound according to an exemplary embodiment of
the present application may be operated by a principle which is
similar to the principle applied to an organic light emitting
device, even in an organic electronic device including an organic
solar cell, an organic photoconductor, an organic transistor, and
the like.
Mode for Invention
Hereinafter, the present specificastion will be described in more
detail through the Examples, but these Examples are provided only
for exemplifying the present application, and are not intended to
limit the scope of the present application.
EXAMPLES
<Preparation Example 1> Preparation of Compound 1-11-2
##STR00120##
1) Preparation of Compound 1-11-2
5.0 g (19.0 mM) of 2-bromodibenzo[b,d]thiophene, 2.6 g (15.8 mM) of
9H--carbazole, 3.0 g (15.8 mM) of CuI, 1.9 mL (15.8 mM) of
trans-1,2-diaminocyclohexane, and 3.3 g (31.6 mM) of
K.sub.3PO.sub.4 were dissolved in 100 mL of 1,4-oxane, and then the
resulting solution was refluxed for 24 hours. After the reaction
was completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM:Hex=1:3) and recrystallized with methanol to obtain 4.7 g
(85%) of Target Compound 1-11-2.
2) Preparation of Compound 1-11-1
7.4 mL (18.6 mM) of 2.5 M n-BuLi was added dropwise to a mixed
solution containing 5 g (14.3 mM) of Compound 1-11-2 and 100 mL of
THF at -78.degree. C., and the resulting mixture was stirred at
room temperature for 1 hour. 4.8 mL (42.9 mM) of trimethyl borate
(B(OMe).sub.3) was added dropwise to the reaction mixture, and the
resulting mixture was stirred at room temperature for 2 hours.
After the reaction was completed, distilled water and DCM were
added thereto at room temperature, extraction was performed, the
organic layer was dried over MgSO.sub.4, and then the solvent was
removed by a rotary evaporator. The reactant was purified by column
chromatography (DCM:MeOH=100:3) and recrystallized with DCM to
obtain 3.9 g (70%) of Target Compound 1-11-1.
3) Preparation of Compound 1-11
7.5 g (19.0 mM) of Compound 1-11-1, 5.1 g (19.0 mM) of
2-chloro-4,6-diphenyl-1,3,5-triazine, 1.1 g (0.95 mM) of
Pd(PPh.sub.3).sub.4, and 5.2 g (38.0 mM) of K.sub.2CO.sub.3 were
dissolved in 100/20/20 mL of toluene/EtOH/H.sub.2O, and then the
resulting solution was refluxed for 12 hours. After the reaction
was completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM:Hex=1:3) and recrystallized with methanol to obtain 7.7 g
(70%) of Target Compound 1-11.
Target Compound A was prepared and synthesized in the same manner
as in the preparation in Preparation Example 1, except that
Intermediate A in the following Table 1 was used instead of
9H-carbazole, and Intermediate B in the following Table 1 was used
instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in Preparation
Example 1.
TABLE-US-00001 TABLE 1 Compound No. Intermediate A Intermediate B
1-2 ##STR00121## ##STR00122## 1-12 ##STR00123## 1-17 ##STR00124##
1-23 ##STR00125## 1-27 ##STR00126## 1-33 ##STR00127## 1-36
##STR00128## 1-39 ##STR00129## ##STR00130## 1-40 ##STR00131## 1-41
##STR00132## 1-42 ##STR00133## 1-46 ##STR00134## ##STR00135## 1-65
##STR00136## ##STR00137## 1-66 ##STR00138## 1-67 ##STR00139## 1-68
##STR00140## 1-69 ##STR00141## 1-70 ##STR00142## 1-71 ##STR00143##
1-72 ##STR00144## 1-76 ##STR00145## ##STR00146## 1-77 ##STR00147##
1-78 ##STR00148## 1-79 ##STR00149## 1-82 ##STR00150## ##STR00151##
1-83 ##STR00152## 1-84 ##STR00153## 1-85 ##STR00154## 1-86
##STR00155## 1-91 ##STR00156## ##STR00157## 1-92 ##STR00158## 1-93
##STR00159## 1-94 ##STR00160## 1-96 ##STR00161## ##STR00162## 1-98
##STR00163## 1-99 ##STR00164## 1-100 ##STR00165## 1-109
##STR00166## ##STR00167## 1-110 ##STR00168## 1-111 ##STR00169##
1-112 ##STR00170## 1-113 ##STR00171## 1-117 ##STR00172##
##STR00173## 1-118 ##STR00174## 1-119 ##STR00175## 1-125
##STR00176## ##STR00177## 1-126 ##STR00178## 1-127 ##STR00179##
1-128 ##STR00180## 1-138 ##STR00181## ##STR00182## 1-176
##STR00183## ##STR00184## 1-177 ##STR00185## 1-178 ##STR00186##
1-179 ##STR00187## 1-180 ##STR00188## 1-181 ##STR00189## Compound
No. Target Compound A Total yield 1-2 ##STR00190## 41% 1-12
##STR00191## 42% 1-17 ##STR00192## 43% 1-23 ##STR00193## 46% 1-27
##STR00194## 45% 1-33 ##STR00195## 43% 1-36 ##STR00196## 41% 1-39
##STR00197## 48% 1-40 ##STR00198## 49% 1-41 ##STR00199## 47% 1-42
##STR00200## 45% 1-46 ##STR00201## 48% 1-65 ##STR00202## 44% 1-66
##STR00203## 46% 1-67 ##STR00204## 47% 1-68 ##STR00205## 44% 1-69
##STR00206## 46% 1-70 ##STR00207## 44% 1-71 ##STR00208## 43% 1-72
##STR00209## 42% 1-76 ##STR00210## 45% 1-77 ##STR00211## 46% 1-78
##STR00212## 47% 1-79 ##STR00213## 48% 1-82 ##STR00214## 49% 1-83
##STR00215## 43% 1-84 ##STR00216## 44% 1-85 ##STR00217## 45% 1-86
##STR00218## 43% 1-91 ##STR00219## 46% 1-92 ##STR00220## 47% 1-93
##STR00221## 47% 1-94 ##STR00222## 44% 1-96 ##STR00223## 46% 1-98
##STR00224## 43% 1-99 ##STR00225## 43% 1-100 ##STR00226## 42% 1-109
##STR00227## 41% 1-110 ##STR00228## 42% 1-111 ##STR00229## 42%
1-112 ##STR00230## 45% 1-113 ##STR00231## 45% 1-117 ##STR00232##
46% 1-118 ##STR00233## 49% 1-119 ##STR00234## 46% 1-125
##STR00235## 43% 1-126 ##STR00236## 44% 1-127 ##STR00237## 45%
1-128 ##STR00238## 42% 1-138 ##STR00239## 47% 1-176 ##STR00240##
48% 1-177 ##STR00241## 49% 1-178 ##STR00242## 44% 1-179
##STR00243## 44% 1-180 ##STR00244## 43% 1-181 ##STR00245## 46%
<Preparation Example 2> Preparation of Compound 1-64
##STR00246##
1) Preparation of Compound 1-64-2
5.0 g (19.0 mM) of 2-bromodibenzo[b,d]thiophene, 5.5 g (19.0 mM) of
(9-phenyl-9H-carbazol-3-yl)boronic acid, 1.1 g (0.95 mM) of
Pd(PPh.sub.3).sub.4, and 5.2 g (38.0 mM) of K.sub.2CO.sub.3 were
dissolved in 100/20/20 mL of toluene/EtOH/H.sub.2O, and then the
resulting solution was refluxed for 12 hours. After the reaction
was completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM:Hex=1:3) and recrystallized with hexane to obtain 5.7 g (70%)
of Target Compound 1-64-2.
2) Preparation of Compound 1-64-1
7.4 mL (18.6 mM) of 2.5 M n-BuLi was added dropwise to a mixed
solution containing 6.1 g (14.3 mM) of Compound 1-64-2 and 100 mL
of THF at -78.degree. C., and the resulting mixture was stirred at
room temperature for 1 hour. 4.8 mL (42.9 mM) of trimethyl borate
(B(OMe).sub.3) was added dropwise to the reaction mixture, and the
resulting mixture was stirred at room temperature for 2 hours.
After the reaction was completed, distilled water and DCM were
added thereto at room temperature, extraction was performed, the
organic layer was dried over MgSO.sub.4, and then the solvent was
removed by a rotary evaporator. The reactant was purified by column
chromatography (DCM:MeOH=100:3) and recrystallized with DCM to
obtain 4.7 g (70%) of Target Compound 1-64-1.
3) Preparation of Compound 1-64
8.9 g (19.0 mM) of Compound 1-64-1, 5.1 g (19.0 mM) of
2-chloro-4,6-diphenyl-1,3,5-triazine, 1.1 g (0.95 mM) of
Pd(PPh.sub.3).sub.4, and 5.2 g (38.0 mM) of K.sub.2CO.sub.3 were
dissolved in 100/20/20 mL of toluene/EtOH/H.sub.2O, and then the
resulting solution was refluxed for 12 hours. After the reaction
was completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM:Hex=1:3) and recrystallized with methanol to obtain 8.7 g
(70%) of Target Compound 1-64.
Target Compound B was prepared and synthesized in the same manner
as in the preparation in Preparation Example 2, except that
Intermediate C in the following Table 2 was used instead of
(9-phenyl-9H-carbazol-3-yl)boronic acid, and Intermediate D in the
following Table 2 was used instead of
2-chloro-4,6-diphenyl-1,3,5-triazine in Preparation Example 2.
TABLE-US-00002 TABLE 2 Compound No. Intermediate C Intermediate D
1-80 ##STR00247## ##STR00248## 1-95 ##STR00249## 1-114 ##STR00250##
1-139 ##STR00251## ##STR00252## 1-140 ##STR00253## ##STR00254##
1-155 ##STR00255## ##STR00256## 1-156 ##STR00257## 1-157
##STR00258## 1-158 ##STR00259## 1-160 ##STR00260## 1-162
##STR00261## 1-163 ##STR00262## 1-164 ##STR00263## 1-165
##STR00264## 1-170 ##STR00265## 1-172 ##STR00266## 1-174
##STR00267## ##STR00268## Compound No. Target Compound B Total
yield 1-80 ##STR00269## 34% 1-95 ##STR00270## 35% 1-114
##STR00271## 37% 1-139 ##STR00272## 36% 1-140 ##STR00273## 38%
1-155 ##STR00274## 40% 1-156 ##STR00275## 39% 1-157 ##STR00276##
39% 1-158 ##STR00277## 37% 1-160 ##STR00278## 36% 1-162
##STR00279## 37% 1-163 ##STR00280## 33% 1-164 ##STR00281## 34%
1-165 ##STR00282## 36% 1-170 ##STR00283## 37% 1-172 ##STR00284##
33% 1-174 ##STR00285## 38%
<Preparation Example 3> Synthesis of Compound 2-2
##STR00286##
1) Preparation of Compound 2-2-2 (Ref 1)
4.2 g (15.8 mM) of 2-bromodibenzo[b,d]thiophene, 6.5 g (15.8 mM) of
9-phenyl-9H,9'H-3,3'-bicarbazole, 3.0 g (15.8 mM) of CuI, 1.9 mL
(15.8 mM) of trans-1,2-diaminocyclohexane, and 3.3 g (31.6 mM) of
K.sub.3PO.sub.4 were dissolved in 100 mL of 1,4-oxane, and then the
resulting solution was refluxed for 24 hours. After the reaction
was completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM:Hex=1:3) and recrystallized with methanol to obtain 7.9 g
(85%) of Target Compound 2-2-2.
2) Preparation of Compound 2-2-1
7.4 mL (18.6 mmol) of 2.5 M n-BuLi was added dropwise to a mixed
solution containing 8.4 g (14.3 mmol) of Compound 2-2-1 and 100 mL
of THF at -78.degree. C., and the resulting mixture was stirred at
room temperature for 1 hour. 4.8 mL (42.9 mmol) of trimethyl borate
was added dropwise to the reaction mixture, and the resulting
mixture was stirred at room temperature for 2 hours. After the
reaction was completed, distilled water and DCM were added thereto
at room temperature, extraction was performed, the organic layer
was dried over MgSO.sub.4, and then the solvent was removed by a
rotary evaporator. The reactant was purified by column
chromatography (DCM:MeOH=100:3) and recrystallized with DCM to
obtain 3.9 g (70%) of Target Compound 2-2-1.
3) Preparation of Compound 2-2
6.7 g (10.5 mM) of Compound 2-2-1, 2.1 g (10.5 mM) of iodobenzene,
606 mg (0.52 mM) of Pd(PPh.sub.3).sub.4, and 2.9 g (21.0 mM) of
K.sub.2CO.sub.3 were dissolved in 100/20/20 mL of
toluene/EtOH/H.sub.2O, and then the resulting solution was refluxed
for 12 hours. After the reaction was completed, distilled water and
DCM were added thereto at room temperature, extraction was
performed, the organic layer was dried over MgSO.sub.4, and then
the solvent was removed by a rotary evaporator. The reactant was
purified by column chromatography (DCM:Hex=1:3) and recrystallized
with methanol to obtain 4.9 g (70%) of Target Compound 2-2.
<Preparation Example 4> Synthesis of Compound 2-3
Target Compound 2-3 (83%) was obtained by performing the
preparation in the same manner as in the preparation of Compound
2-2, except that 4-iodo-1,1'-biphenyl was used instead of
iodobenzene in the preparation of Compound 2-2.
<Preparation Example 5> Synthesis of Compound Ref 2
##STR00287##
1) Preparation of Compound ref 2-2
88.0 mL (157.8 mM) of 1.8 M LDA was added dropwise to a mixed
solution containing 30.0 g (121.4 mM) of 2-bromodibenzofuran and
300 mL of THF at -78.degree. C., and the resulting mixture was
stirred at room temperature for 1 hour. 11.0 g (42.9 mmol) of
iodine was put into the reaction mixture, and the resulting mixture
was stirred at room temperature for 2 hours. After the reaction was
completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM) and recrystallized with MeOH to obtain 23.1 g (51%) of Target
Compound ref 2-2.
2) Preparation of Compound Ref 2-1
3.9 g (10.5 mM) of Compound ref 2-2, 1.3 g (10.5 mM) of
phenylboronic acid, 606 mg (0.52 mM) of Pd(PPh.sub.3).sub.4, and
2.9 g (21.0 mM) of K.sub.2CO.sub.3 were dissolved in 100/20/20 mL
of toluene/EtOH/H.sub.2O, and then the resulting solution was
refluxed for 12 hours. After the reaction was completed, distilled
water and DCM were added thereto at room temperature, extraction
was performed, the organic layer was dried over MgSO.sub.4, and
then the solvent was removed by a rotary evaporator. The reactant
was purified by column chromatography (DCM:Hex=1:3) and
recrystallized with methanol to obtain 2.4 g (70%) of Target
Compound ref 2-1.
3) Preparation of Compound ref 2
5.1 g (15.8 mM) of Compound ref 2-1, 6.5 g (15.8 mM) of
9-phenyl-9H,9'H-3,3'-bicarbazole, 3.0 g (15.8 mM) of CuI, 1.9 mL
(15.8 mM) of trans-1,2-diaminocyclohexane, and 3.3 g (31.6 mM) of
K.sub.3PO.sub.4 were dissolved in 100 mL of 1,4-oxane, and then the
resulting solution was refluxed for 24 hours. After the reaction
was completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM:Hex=1:3) and recrystallized with methanol to obtain 8.7 g
(85%) of Target Compound ref 2.
<Preparation Example 6> Preparation of Compound Ref 3
##STR00288##
5.5 g (19.0 mmol) of (3-(9H-carbazol-9-yl)phenyl)boronic acid, 5.1
g (19.0 mM) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.1 g (0.95
mM) of Pd(PPh.sub.3).sub.4, and 5.2 g (38.0 mM) of K.sub.2CO.sub.3
were dissolved in 100/20/20 mL of toluene/ethanol/H.sub.2O, and
then the resulting solution was refluxed for 12 hours. After the
reaction was completed, distilled water and DCM were added thereto
at room temperature, extraction was performed, the organic layer
was dried over MgSO.sub.4, and then the solvent was removed by a
rotary evaporator. The reactant was purified by column
chromatography (DCM:Hex=1:3) and recrystallized with methanol to
obtain 6.3 g (70%) of Target Compound ref 3.
<Preparation Example 7> Synthesis of Compound 2-7
Compound 2-7 was obtained by using 2-bromo-9,9-dimethyl-9H-fluorene
instead of iodobenzene in the preparation of Compound 2-2 (yield
69%).
<Preparation Example 8> Synthesis of Compound 2-9
Compound 2-9 was obtained by using 2-bromodibenzo[b,d]thiophene
instead of iodobenzene in the preparation of Compound 2-2 (yield
72%).
<Preparation Example 9> Synthesis of Compound 2-11
Compound 2-11 was obtained by using 2-bromodibenzo[b,d]furan
instead of iodobenzene in the preparation of Compound 2-2 (yield
68%).
<Preparation Example 10> Preparation of Compound Ref 4
##STR00289##
5.5 g (19.0 mmol) of (3-(9H-carbazol-9-yl)phenyl)boronic acid, 5.1
g (19.0 mM) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.1 g (0.95
mM) of Pd(PPh.sub.3).sub.4, and 5.2 g (38.0 mM) of K.sub.2CO.sub.3
were dissolved in 100/20/20 mL of toluene/ethanol/H.sub.2O, and
then the resulting solution was refluxed for 12 hours. After the
reaction was completed, distilled water and DCM were added thereto
at room temperature, extraction was performed, the organic layer
was dried over MgSO.sub.4, and then the solvent was removed by a
rotary evaporator. The reactant was purified by column
chromatography (DCM:Hex=1:3) and recrystallized with methanol to
obtain 6.3 g (70%) of Compound ref 4.
<Preparation Example 11> Preparation of Compound Ref 5
##STR00290##
5.8 g (19.0 mM) of (3-(dibenzo[b,d]thiophene-4-yl)phenyl)boronic
acid, 5.1 g (19.0 mM) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.1
g (0.95 mM) of Pd(PPh.sub.3).sub.4, and 5.2 g (38.0 mM) of
K.sub.2CO.sub.3 were dissolved in 100/20/20 mL of
toluene/ethanol/H.sub.2O, and then the resulting solution was
refluxed for 12 hours. After the reaction was completed, distilled
water and DCM were added thereto at room temperature, extraction
was performed, the organic layer was dried over MgSO.sub.4, and
then the solvent was removed by a rotary evaporator. The reactant
was purified by column chromatography (DCM:Hex=1:3) and
recrystallized with methanol to obtain 6.5 g (70%) of Compound ref
5.
<Preparation Example 12> Synthesis of Compound Ref 6
##STR00291##
1) Preparation of Compound ref 6-2
11.4 mL (22.8 mM) of 2.0 M lithium diisopropylamine was added
dropwise to a mixed solution containing 4.7 g (19.0 mM) of
2-bromodibenzo[b,d]furan and 100 mL of THF at -78.degree. C., and
the resulting mixture was stirred at -78.degree. C. for 1 hour. 4.8
mL (42.9 mM) of trimethyl borate was added dropwise to the reaction
mixture, and the resulting mixture was stirred at room temperature
for 2 hours. After the reaction was completed, distilled water and
DCM were added thereto at room temperature, extraction was
performed, the organic layer was dried over MgSO.sub.4, and then
the solvent was removed by a rotary evaporator. The reactant was
purified by column chromatography (DCM:MeOH=100:3) and
recrystallized with DCM to obtain 3.9 g (70%) of Compound ref
6-2.
2) Preparation of Compound Ref 6-1
5.5 g (19.0 mM) of Compound ref 6-2, 5.9 g (19.0 mM) of
2-bromo-4,6-diphenylpyrimidine, 1.1 g (0.95 mM) of
Pd(PPh.sub.3).sub.4, and 5.2 g (38.0 mM) of K.sub.2CO.sub.3 were
dissolved in 100/20/20 mL of toluene/ethanol/H.sub.2O, and then the
resulting solution was refluxed for 12 hours. After the reaction
was completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM:Hex=1:3) and recrystallized with hexane to obtain 6.3 g (70%)
of Compound ref 6-1.
3) Preparation of Compound Ref 6
9.1 g (19.0 mM) of Compound ref 6-1, 4.5 g (15.8 mM) of
7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole, 3.0 g (15.8 mM) of
CuI, 1.9 mL (15.8 mM) of trans-1,2-diaminocyclohexane, and 3.3 g
(31.6 mM) of K.sub.3PO.sub.4 were dissolved in 100 mL of 1,4-oxane,
and then the resulting solution was refluxed for 24 hours. After
the reaction was completed, distilled water and DCM were added
thereto at room temperature, extraction was performed, the organic
layer was dried over MgSO.sub.4, and then the solvent was removed
by a rotary evaporator. The reactant was purified by column
chromatography (DCM:Hex=1:3) and recrystallized with methanol to
obtain 9.1 g (85%) of Compound ref 6.
<Preparation Example 13> Synthesis of Compound Ref 7
##STR00292##
1) Preparation of Compound Ref 7-2
5.0 g (19.0 mM) of 4-bromodibenzo[b,d]thiophene, 2.6 g (15.8 mM) of
9H-carbazole, 3.0 g (15.8 mM) of CuI, 1.9 mL (15.8 mM) of
trans-1,2-diaminocyclohexane, and 3.3 g (31.6 mM) of
K.sub.3PO.sub.4 were dissolved in 100 mL of 1,4-oxane, and then the
resulting solution was refluxed for 24 hours. After the reaction
was completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM:Hex=1:3) and recrystallized with methanol to obtain 4.7 g
(85%) of Compound ref 7-2.
2) Preparation of Compound Ref 7-1
7.4 mL (18.6 mM) of 2.5 M n-BuLi was added dropwise to a mixed
solution containing 5.0 g (14.3 mM) of Compound ref 7-2 and 100 mL
of THF at -78.degree. C., and the resulting mixture was stirred at
room temperature for 1 hour. 4.8 mL (42.9 mM) of trimethyl borate
was added dropwise to the reaction mixture, and the resulting
mixture was stirred at room temperature for 2 hours. After the
reaction was completed, distilled water and DCM were added thereto
at room temperature, extraction was performed, the organic layer
was dried over MgSO.sub.4, and then the solvent was removed by a
rotary evaporator. The reactant was purified by column
chromatography (DCM:MeOH=100:3) and recrystallized with DCM to
obtain 3.9 g (70%) of Target Compound ref 7-1.
3) Preparation of Compound Ref 7
7.5 g (19.0 mM) of Compound ref 7-1, 5.1 g (19.0 mM) of
2-chloro-4,6-diphenyl-1,3,5-triazine, 1.1 g (0.95 mM) of
Pd(PPh.sub.3).sub.4, and 5.2 g (38.0 mM) of K.sub.2CO.sub.3 were
dissolved in 100/20/20 mL of toluene/ethanol/H.sub.2O, and then the
resulting solution was refluxed for 12 hours. After the reaction
was completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM:Hex=1:3) and recrystallized with methanol to obtain 7.7 g
(70%) of Compound ref 7.
<Preparation Example 14> Synthesis of Compound Ref 8
##STR00293##
5.0 g (19.0 mM) of 2-bromodibenzo[b,d]thiophene, 4.5 g (15.8 mM) of
7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole, 3.0 g (15.8 mM) of
CuI, 1.9 mL (15.8 mM) of trans-1,2-diaminocyclohexane, and 3.3 g
(31.6 mM) of K.sub.3PO.sub.4 were dissolved in 100 mL of 1,4-oxane,
and then the resulting solution was refluxed for 24 hours. After
the reaction was completed, distilled water and DCM were added
thereto at room temperature, extraction was performed, the organic
layer was dried over MgSO.sub.4, and then the solvent was removed
by a rotary evaporator. The reactant was purified by column
chromatography (DCM:Hex=1:3) and recrystallized with methanol to
obtain 7.3 g (85%) of Compound ref 8.
<Preparation Example 15> Synthesis of Compound Ref 9
##STR00294##
4.2 g (15.8 mM) of 2-bromodibenzo[b,d]thiophene, 6.5 g (15.8 mM) of
9-phenyl-9H,9'H-3,3'-bicarbazole, 3.0 g (15.8 mM) of CuI, 1.9 mL
(15.8 mM) of trans-1,2-diaminocyclohexane, and 3.3 g (31.6 mM) of
K.sub.3PO.sub.4 were dissolved in 100 mL of 1,4-oxane, and then the
resulting solution was refluxed for 24 hours. After the reaction
was completed, distilled water and DCM were added thereto at room
temperature, extraction was performed, the organic layer was dried
over MgSO.sub.4, and then the solvent was removed by a rotary
evaporator. The reactant was purified by column chromatography
(DCM:Hex=1:3) and recrystallized with methanol to obtain 7.9 g
(85%) of Compound ref 9.
Compounds were prepared in the same manner as in the Preparation
Examples, and the synthesis confirmation results thereof are shown
in Tables 3 to 23.
TABLE-US-00003 TABLE 3 HOMO = -5.5 - (E.sub.ox(Compound 1-2) -
E.sub.ox(NPB)) (eV) Band gap = 1240/UV absorption edge(404 nm) (eV)
E.sub.ox HOMO Band gap LUMO NPB 0.81 Compound 1-2 1.45 -6.14 3.07
-3.07
TABLE-US-00004 TABLE 4 HOMO = - 5.5 - (E.sub.ox(Compound 1-11) -
E.sub.ox(NPB)) (eV) Band gap = 1240/UV absorption edge(432 nm) (eV)
E.sub.ox HOMO Band gap LUMO NPB 0.80 Compound 1-11 1.48 -6.18 2.87
-3.31
TABLE-US-00005 TABLE 5 HOMO = -5.5 - (E.sub.ox(Compound 1-23) -
E.sub.ox(NPB)) (eV) Band gap = 1240/UV absorption edge(367 nm) (eV)
E.sub.ox HOMO Band gap LUMO NPB 0.82 Compound 1-23 1.38 -6.06 3.38
-2.68
TABLE-US-00006 TABLE 6 HOMO = -5.5 - (E.sub.ox(Compound 1-27) -
E.sub.ox(NPB)) (eV) Band gap = 1240/UV absorption edge(369 nm) (eV)
E.sub.ox HOMO Band gap LUMO NPB 0.80 Compound 1-27 1.37 -6.07 3.36
-2.71
TABLE-US-00007 TABLE 7 HOMO = -5.5 - (E.sub.ox(Compound 1-33) -
E.sub.ox(NPB)) (eV) Band gap = 1240/UV absorption edge(378 nm) (eV)
E.sub.ox HOMO Band gap LUMO NPB 0.83 Compound 1-33 1.45 -6.11 3.28
-3.82
TABLE-US-00008 TABLE 8 HOMO = -5.5 - (E.sub.ox(Compound 1-39) -
E.sub.ox(NPB)) (eV) Band gap = 1240/UV absorption edge(433 nm) (eV)
E.sub.ox HOMO Band gap LUMO NPB 0.76 Compound 1-39 1.41 -6.15 2.86
-3.29
TABLE-US-00009 TABLE 9 HOMO = -5.5 - (E.sub.ox(Compound 1-41) -
E.sub.ox(NPB)) (eV) Band gap = 1240/UV absorption edge(366 nm) (eV)
E.sub.ox HOMO Band gap LUMO NPB 0.78 Compound 1-41 1.40 -6.12 3.39
-2.73
TABLE-US-00010 TABLE 10 HOMO = -5.5 - (E.sub.ox(Compound 1-65) -
E.sub.ox(NPB)) (eV) Band gap = 1240/UV absorption edge(416 nm) (eV)
E.sub.ox HOMO Band gap LUMO NPB 0.79 Compound 1-65 1.22 -5.93 2.98
-2.95
TABLE-US-00011 TABLE 11 HOMO = -5.5 - (E.sub.ox (Compound 1-66) -
E.sub.ox (NPB)) (eV) Band gap = 1240/UV absorption edge (425 nm)
(eV) E.sub.ox HOMO Band gap LUMO NPB 0.77 Compound 1-66 1.19 -5.93
2.92 -3.01
TABLE-US-00012 TABLE 12 HOMO = -5.5 - (E.sub.ox (Compound 1-67) -
E.sub.ox (NPB)) (eV) Band gap = 1240/UV absorption edge (452 nm)
(eV) E.sub.ox HOMO Band gap LUMO NPB 0.76 Compound 1-67 1.16 -5.89
2.74 -3.15
TABLE-US-00013 TABLE 13 HOMO = -5.5 - (E.sub.ox (Compound 1-69) -
E.sub.ox (NPB)) (eV) Band gap = 1240/UV absorption edge (371 nm)
(eV) E.sub.ox HOMO Band gap LUMO NPB 0.78 Compound 1-69 1.13 -5.86
3.34 -2.52
TABLE-US-00014 TABLE 14 HOMO = -5.5 - (E.sub.ox (Compound 1-70) -
E.sub.ox (NPB)) (eV) Band gap = 1240/UV absorption edge (371 nm)
(eV) E.sub.ox HOMO Band gap LUMO NPB 0.76 Compound 1-70 1.14 -5.88
3.34 -2.54
TABLE-US-00015 TABLE 15 HOMO = -5.5 - (E.sub.ox (Compound 1-71) -
E.sub.ox (NPB)) (eV) Band gap = 1240/UV absorption edge (371 nm)
(eV) E.sub.ox HOMO Band gap LUMO NPB 0.77 Compound 1-71 1.15 -5.88
3.34 -2.54
TABLE-US-00016 TABLE 16 HOMO = -5.5 - (E.sub.ox (Compound 1-78) -
E.sub.ox (NPB)) (eV) Band gap = 1240/UV absorption edge (438 nm)
(eV) E.sub.ox HOMO Band gap LUMO NPB 0.78 Compound 1-78 1.30 -6.02
2.83 -3.19
TABLE-US-00017 TABLE 17 HOMO = -5.5 - (E.sub.ox (Compound 1-82) -
E.sub.ox (NPB)) (eV) Band gap = 1240/UV absorption edge (426 nm)
(eV) E.sub.ox HOMO Band gap LUMO NPB 0.78 Compound 1-82 1.09 -5.81
2.91 -2.90
TABLE-US-00018 TABLE 18 HOMO = -5.5 - (E.sub.ox (Compound 1-84) -
E.sub.ox (NPB)) (eV) Band gap = 1240/UV absorption edge (463 nm)
(eV) E.sub.ox HOMO Band gap LUMO NPB 0.77 Compound 1-84 1.08 -5.80
2.68 -3.12
TABLE-US-00019 TABLE 19 HOMO = -5.5 - (E.sub.ox (Compound 1-99) -
E.sub.ox (NPB)) (eV) Band gap = 1240/UV absorption edge (364 nm)
(eV) E.sub.ox HOMO Band gap LUMO NPB 0.83 Compound 1-99 1.36 -6.03
3.41 -2.62
TABLE-US-00020 TABLE 20 Td (signal value: 95%) Tg Compound 1-2
442.04.degree. C. -- Compound 1-11 426.38.degree. C. -- Compound
1-23 473.62.degree. C. 141.91.degree. C. Compound 1-27
464.07.degree. C. -- Compound 1-33 478.83.degree. C. 153.06.degree.
C. Compound 1-39 460.32.degree. C. 151.88.degree. C. Compound 1-41
484.24.degree. C. 157.88.degree. C. Compound 1-65 467.84.degree. C.
179.13.degree. C. Compound 1-66 463.00.degree. C. 179.38.degree. C.
Compound 1-67 461.79.degree. C. 185.05.degree. C. Compound 1-69
492.45.degree. C. 179.99.degree. C. Compound 1-70 482.96.degree. C.
185.05.degree. C. Compound 1-71 461.10.degree. C. 169.72.degree. C.
Compound 1-78 462.82.degree. C. 180.63.degree. C. Compound 1-82
495.17.degree. C. -- Compound 1-84 492.52.degree. C. 188.83.degree.
C. Compound 1-99 523.67.degree. C. 176.50.degree. C.
TABLE-US-00021 TABLE 21 Compound .sup.1H NMR (CDCl.sub.3, 200 Mz)
1-2 .delta. = 9.26 (1H, d), 8.51 (1H, d), 8.41~8.39 (4H, m), 8.23
(2H, d), 8.18 (1H, d), 8.13 (1H, s), 8.06 (1H, d), 7.62~7.43 (12H,
m), 7.34 (2H, t) 1-11 .delta. = 9.32 (1H, d), 8.90~8.88 (4H, m),
8.61 (1H, d), 8.25 (2H, d), 8.21 (1H, d), 8.12 (1H, d), 7.65~7.45
(12H, m), 7.37 (2H, t) 1-12 .delta. = 8.55 (1H, d), 8.45~8.36 (4H,
m), 8.19 (1H, d), 7.93~8.00 (4H, m), 7.73~7.77 (4H, m), 7.35~7.61
(12H, m), 7.20~7.20 (2H, m) 1-17 .delta. = 8.55 (1H, d), 8.45 (1H,
d), 8.30 (2H, d), 7.90~8.12 (6H, m), 7.78 (1H, t), 7.47~7.69 (10H,
m), 7.25~7.33 (3H, m) 1-23 .delta. = 8.55 (1H, d), 8.45~8.38 (2H,
m), 8.23~8.19 (2H, m), 8.00~7.93 (8H, m), 7.77~7.73 (2H, m),
7.58~7.49 (11H, m), 7.35 (1H, t), 7.20~7.16 (2H, m) 1-27 .delta. =
9.27 (1H, s), 8.89 (1H, d), 8.79 (4H, m), 8.41 (1H, d), 8.21 (3H,
m), 8.05 (1H, d), 7.93 (1H, d), 7.87 (1H, d), 7.77 (1H, t),
7.64~7.46 (12H, m), 7.32 (2H, t) 1-33 .delta. = 8.92 (2H, d), 8.36
(1H, d), 8.32 (4H, m), 8.21~8.16 (3H, m), 8.07 (1H, s), 8.01 (2H,
d), 7.94 (1H, d), 7.61~7.44 (12H, m), 7.32 (2H, t) 1-36 .delta. =
8.55 (1H, d), 8.45 (1H, d), 8.36 (4H, d), 8.19 (1H, d), 8.00~7.93
(5H, m), 7.77 (1H, s), 7.58~7.49 (10H, m), 7.35 (1H, t), 7.25~7.16
(4H, m) 1-39 .delta. = 9.35 (1H, s), 8.90 (4H, d), 8.64 (1H, s),
8.30~8.20 (3H, m), 8.13 (1H, d), 7.71 (1H, s), 7.66~7.45 (14H, m),
7.38~7.33 (3H, m) 1-40 .delta. = 9.38 (1H, s), 9.24 (1H, s), 8.87
(3H, d), 8.64 (1H, s), 8.30~8.21 (3H, m), 8.08 (1H, d), 7.90 (1H,
d), 7.80 (2H, d), 7.72~7.32 (19H, d) 1-41 .delta. = 9.30 (1H, s),
8.90 (1H, d), 8.80 (4H, d), 8.43 (1H, s), 8.26~8.20 (3H, m), 8.03
(1H, d), 7.93 (1H, d), 7.87 (1H, s), 7.77 (1H, t), 7.72 (1H, s),
7.67 (1H, d), 7.60~7.47 (11H, m), 7.41~7.29 (4H, m) 1-42 .delta. =
8.55 (1H, d), 8.45 (1H, d), 8.36~8.31 (5H, m), 8.00~7.91 (6H, m),
7.77~7.74 (4H, m), 7.56~7.35 (12H, m), 7.25 (2H, d), 7.16 (1H, t)
1-46 .delta. = 8.62 (1H, d), 8.45 (1H, d), 8.36~8.31 (5H, m), 8.22
(1H, m), 8.00 (1H, s), 7.93~7.91 (2H, m), 7.77~7.74 (7H, m),
7.50~7.41 (14H, m) 1-64 .delta. = 8.55 (1H, d), 8.45 (1H, d), 8.36
(4H, d), 8.22 (1H, s), 7.99~7.89 (5H, m), 7.77 (1H, d), 7.62~7.49
(13H, m), 7.35 (1H, t), 7.16 (1H, t) 1-65 .delta. = 9.33 (1H, d),
8.59 (1H, d), 8.53 (1H, s), 8.42 (4H, m), 8.28 (1H, d), 8.22 (1H,
d), 8.15 (1H, s), 8.09 (1H, d), 7.90 (1H, d), 7.59~7.51 (10H, m),
7.50~7.34 (4H, m), 7.17 (1H, m), 1.53~1.50 (6H, d) 1-66 .delta. =
8.96 (2H, d), 8.60 (1H, s), 8.53 (1H, s), 8.46 (1H, s), 8.29~8.23
(4H, m), 8.19 (1H, s), 8.10 (1H, d), 7.90 (1H, d), 7.66~7.59 (4H,
m), 7.56~7.51 (4H, m), 7.47~7.38 (6H, m), 7.31 (1H, m), 1.53~1.50
(6H, d) 1-67 .delta. = 9.39 (1H, s), 8.90 (4H, d), 8.68 (1H, s),
8.54 (1H, s), 8.30 (1H, d), 8.25 (1H, d), 8.15 (1H, d), 7.91 (1H,
d), 7.64~7.52 (10H, m), 7.47~7.35 (4H, m), 7.29 (1H, t), 1.53~1.50
(6H, d) 1-68 .delta. = 8.55 (1H, d), 8.45 (1H, d), 8.24 (1H, d),
7.94~7.88 (3H, m), 7.80~7.74 (4H, m), 7.57~7.49 (7H, m), 7.38~7.33
(3H, m), 7.24~7.16 (4H, m), 7.05 (1H, m), 1.69 (6H, s) 1-69 .delta.
= 9.26 (1H, s), 8.84 (1H, d), 8.49 (1H, s), 8.43 (1H, s), 8.31 (4H,
m), 8.25~8.20 (2H, m), 8.07 (1H, s), 7.95 (2H, t), 7.88 (2H, s),
7.73 (1H, t), 7.55 (10H, m), 7.45~7.28 (5H, m), 1.53~1.50 (6H, d)
1-70 .delta. = 9.26 (1H, s), 8.84 (1H, d), 8.49 (1H, s), 8.43 (1H,
s), 8.31 (4H, m), 8.25~8.20 (2H, m), 8.07 (1H, s), 7.71 (1H, t),
7.55 (10H, m), 7.45~7.28 (5H, m), 1.53~1.50 (6H, d) 1-71 .delta. =
8.54 (1H, s), 8.33 (1H, s), 8.30 (1H, d), 8.15 (1H, d), 7.96 (1H,
d), 7.89 (4H, t), 7.78 (1H, s), 7.59~7.50 (3H, m), 7.44~7.25 (11H,
m), 7.23~7.14 (4H, m), 6.85 (1H, t), 1.53~1.50 (6H, d) 1-72 .delta.
= 8.55 (1H, d), 8.45 (1H, d), 8.24~8.23 (2H, m), 8.00~7.88 (10H,
m), 7.77~7.74 (2H, m), 7.56~7.49 (10H, m), 7.38~7.35 (2H, m), 7.25
(2H, d), 7.16 (1H, t), 1.69 (6H, s) 1-78 .delta. = 9.36 (1H, s),
8.89 (2H, d), 8.64 (1H, s), 8.27~8.21 (3H, m), 8.13 (1H, d), 7.79
(1H, s), 7.67~7.50 (9H, m), 7.47~7.35 (4H, m), 7.30~7.17 (2H, m),
1.69 (6H, s) 1-82 .delta. = 9.31 (1H, s), 8.92 (1H, s), 8.57 (1H,
s), 8.43 (4H, m), 8.35 (1H, d), 8.31 (1H, d), 8.18 (2H, m), 8.05
(1H, d), 7.63~7.47 (11H, m), 7.45~7.28 (7H, m), 7.20 (1H, m) 1-83
.delta. = 8.55 (1H, d), 8.45 (1H, d), 8.35 (2H, d), 8.23~8.19 (2H,
m), 8.00~7.93 (5H, m), 7.77 (1H, s), 7.62~7.49 (16H, m), 7.40~7.35
(2H, m), 7.20~7.16 (2H, m) 1-84 .delta. = 9.39 (1H, s), 8.92 (1H,
s), 8.90 (4H, m), 8.62 (1H, s), 8.37~8.33 (2H, m), 8.19 (1H, d),
8.11 (1H, d), 7.67~7.47 (11H, m), 7.45~7.28 (7H, m), 7.30 (2H, m),
7.20 (1H, m) 1-93 .delta. = 8.55 (1H, d), 8.45 (1H, d), 8.28 (4H,
d), 8.12 (1H, d), 7.90~7.98 (3H, m), 7.29~7.69 (21H, m) 1-96
.delta. = 8.55 (1H, d), 8.45 (2H, m), 8.23 (1H, s), 7.90~8.08 (5H,
m), 7.79 (4H, d), 7.69 (1H, s), 7.25~7.52 (13H, m) 1-98 .delta. =
8.55 (1H, d), 8.45 (1H, d), 8.36 (4H, d), 8.05~7.93 (5H, m), 7.77
(1H, s), 7.56~7.49 (10H, m), 7.35~7.33 (2H, m), 7.16 (1H, t) 1-99
.delta. = 9.25 (1H, s), 8.85 (1H, d), 8.45 (1H, s), 8.38 (1H, d),
8.32 (4H, m), 8.22 (3H, m), 8.07 (1H, s), 8.00 (2H, t), 7.94 (2H,
m), 7.76~7.66 (3H, m), 7.66~7.47 (12H, m) 1-100 .delta. = 8.55 (1H,
d), 8.45 (2H, m), 8.28 (4H, d), 8.24 (1H, d), 7.90~8.05 (5H, m),
7.69~7.70 (2H, m), 7.23~7.57 (15H, m) 1-110 9.31 (1H, s), 9.29 (1H,
s), 8.81 (4H, d), 8.30~8.58 (7H, m), 7.30~7.79 (13H, m) 1-117
.delta. = 8.55 (1H, d), 8.45 (1H, d), 8.28 (4H, d), 7.89~7.94 (5H,
m), 7.66~7.69 (2H, m), 7.25~7.52 (12H, m), 7.13 (1H, d) 1-119
.delta. = 8.57 (1H, d), 8.46 (1H, d), 8.28 (4H, d), 8.24 (1H, d),
7.89~7.98 (5H, m), 7.66~7.70 (3H, m), 7.25~7.57 (14H, m), 7.13 (1H,
d) 1-126 .delta. = 8.56 (1H, d), 8.45 (1H, d), 8.28 (4H, d),
7.89~7.98 (5H, m), 7.66~7.69 (2H, m), 7.25~7.53 (13H, m) 1-163
.delta. = 8.55 (1H, d), 8.45 (1H, d), 8.36 (4H, d), 8.22~8.19 (2H,
m), 7.99~7.91 (8H, m), 7.58~7.49 (10H, m), 7.35 (1H, t), 7.20~7.16
(2H, m) 1-170 .delta. = 8.55 (1H, d), 8.45 (2H, m), 8.28 (4H, d),
7.94~8.05 (5H, m), 7.75~7.79 (3H, m), 7.68 (2H, d), 7.25~7.53 (13H,
m) 1-172 .delta. = 8.57 (1H, d), 8.45 (1H, d), 8.28 (4H, d),
7.89~7.98 (5H, m), 7.66~7.79 (6H, m), 7.25~7.52 (12H, m) 1-176
.delta. = 8.58 (1H, d), 8.45 (1H, d), 8.16 (1H, d), 7.79~7.94 (9H,
m), 7.25~7.69 (12H, m) 1-177 .delta. = 8.55 (1H, d), 8.45~8.46 (2H,
m), 8.16 (1H, d), 7.83~8.05 (9H, m), 7.69 (1H, s), 7.25~7.58 (11H,
m) 1-178 .delta. = 8.55 (1H, d), 8.45 (1H, d), 8.09~8.16 (2H, m),
7.79~7.98 (7H, m), 7.24~7.69 (13H, m), 1.72 (6H, s) 1-179 .delta. =
8.57 (1H, d), 8.47 (1H, d), 8.09~8.16 (3H, m), 7.79~7.98 (7H, m),
7.69 (1H, s), 7.24~7.61 (12H, m), 1.72 (6H, s) 1-180 .delta. = 8.54
(1H, d), 8.44~8.46 (2H, m), 8.16 (1H, d), 7.79~8.05 (9H, m), 7.69
(1H, s), 7.25~7.60 (11H, m) 1-181 .delta. = 8.55 (1H, d), 8.45 (1H,
d), 8.16 (1H, d), 7.79~7.98 (9H, m), 7.25~7.69 (13H, m) 2-2 .delta.
= 8.55 (1H, d), 8.45 (1H, d), 8.30 (1H, d), 8.19 (1H, d), 8.13 (1H,
d), 8.00~7.89 (6H, m), 7.77 (2H, m), 7.62~7.35 (15H, m), 7.20~7.16
(2H, m) 2-3 .delta. = 8.55 (1H, d), 8.45 (1H, d), 8.30 (1H, d),
8.19 (1H, d), 8.13 (1H, d), 8.00~7.89 (6H, m), 7.77 (4H, m),
7.62~7.41 (13H, m), 7.25~7.16 (6H, m) 2-7 .delta. = 8.55 (1H, d),
8.45 (1H, d), 8.30 (1H, d), 8.19~8.09 (3H, m), 8.00~7.89 (8H, m),
7.78~7.77 (3H, m), 7.62~7.49 (10H, m), 7.38~7.16 (5H, m), 1.69 (6H,
s) 2-9 .delta. = 8.55 (1H, d), 8.45 (2H, d), 8.30 (1H, d),
8.19~8.12 (4H, m), 8.00~7.89 (8H, m), 7.77 (2H, m), 7.62~7.49 (11H,
m), 7.35 (1H, t), 7.21~7.16 (2H, m) 2-11 .delta. = 8.55 (1H, d),
8.45 (1H, d), 8.30 (1H, d), 8.19 (1H, d), 8.13 (1H, d), 8.00~7.77
(12H, m), 7.62~7.31 (13H, m), 7.20~7.16 (2H, m)
TABLE-US-00022 TABLE 22 Com- Com- pound FD-MS pound FD-MS 1-2 m/z =
579.18 1-11 m/z = 580.17 (C.sub.40H.sub.25N.sub.3S = 579.72)
(C.sub.39H.sub.24N.sub.4S = 580.71) 1-12 m/z = 656.20 1-17 m/z =
552.17 (C.sub.45H.sub.28N4S = 656.81) (C.sub.39H.sub.24N.sub.2S =
552.69) 1-23 m/z = 655.21 1-27 m/z = 656.20
(C.sub.46H.sub.29N.sub.3S = 655.81) (C.sub.45H.sub.28N.sub.4S =
656.80) 1-33 m/z = 655.21 1-36 m/z = 656.20
(C.sub.46H.sub.29N.sub.3S = 655.81) (C.sub.45H.sub.28N.sub.4S =
656.80) 1-39 m/z = 656.20 1-40 m/z = 732.23 (C.sub.45H.sub.28N4S =
656.80) (C.sub.51H.sub.32N.sub.4S = 732.90) 1-41 m/z = 732.23 1-42
m/z = 732.23 (C.sub.51H.sub.32N.sub.4S = 732.89)
(C.sub.51H.sub.32N.sub.4S = 732.89) 1-46 m/z = 732.23 1-64 m/z =
656.20 (C.sub.51H.sub.32N.sub.4S = 732.89)
(C.sub.45H.sub.28N.sub.4S = 656.80) 1-65 m/z = 695.24 1-66 m/z =
695.24 (C.sub.49H.sub.33N.sub.3S = 695.87)
(C.sub.49H.sub.33N.sub.3S = 695.87) 1-67 m/z = 696.23 1-68 m/z =
669.22 (C.sub.48H.sub.32N.sub.4S = 696.86)
(C.sub.47H.sub.31N.sub.3S = 669.83) 1-69 m/z = 771.27 1-70 m/z =
772.27 (C.sub.55H.sub.37N.sub.3S = 771.97)
(C.sub.54H.sub.36N.sub.4S = 772.96) 1-71 m/z = 733.26 1-72 m/z =
772.27 (C.sub.52H.sub.35N.sub.3S = 733.93)
(C.sub.54H.sub.36N.sub.4S = 772.96) 1-78 m/z = 696.23 1-82 m/z =
744.23 (C.sub.48H.sub.32N.sub.4S = 696.86)
(C.sub.52H.sub.32N.sub.4S = 744.90) 1-83 m/z = 744.23 1-84 m/z =
745.23 (C.sub.52H.sub.32N.sub.4S = 744.90)
(C.sub.51H.sub.31N.sub.5S = 745.89) 1-93 m/z = 745.23 1-96 m/z =
685.16 (C.sub.51H.sub.31N.sub.5S = 745.89)
(C.sub.46H.sub.27N.sub.3S.sub.2 = 685.86) 1-98 m/z = 686.16 1-99
m/z = 761.20 (C.sub.45H.sub.26N.sub.4S.sub.2 = 686.84)
(C.sub.51H.sub.31N.sub.3S.sub.2 = 761.95) 1-100 m/z = 762.19 1-110
m/z = 686.16 (C.sub.51H.sub.30N.sub.4S.sub.2 = 762.94)
(C.sub.45H.sub.26N.sub.4S.sub.2 = 686.84) 1-117 m/z = 670.18 1-119
m/z = 746.21 (C.sub.45H.sub.26N.sub.4OS = 670.78)
(C.sub.51H.sub.30N.sub.4OS = 746.88) 1-126 m/z = 670.18 1-163 m/z =
656.80 (C.sub.45H.sub.26N.sub.4OS = 670.78)
(C.sub.45H.sub.28N.sub.4S = 656.20) 1-170 m/z = 762.19 1-172 m/z =
746.21 (C.sub.51H.sub.30N.sub.4S.sub.2 = 762.94)
(C.sub.51H.sub.30N.sub.4OS = 746.88) 1-176 m/z = 643.17 1-177 m/z =
659.15 (C.sub.44H.sub.25N.sub.3OS = 643.75)
(C.sub.44H.sub.25N.sub.3S.sub.2 = 659.82) 1-178 m/z = 669.22 1-179
m/z = 669.22 (C.sub.47H.sub.31N.sub.3S = 669.83)
(C.sub.47H.sub.31N.sub.3S = 669.83) 1-180 m/z = 659.15 1-181 m/z =
643.17 (C.sub.44H.sub.25N.sub.3S.sub.2 = 659.82)
(C.sub.44H.sub.25N.sub.3OS = 643.75)
TABLE-US-00023 TABLE 23 Compound FD-Mass Compound FD-Mass 2-1 m/z =
742.94 (C54H34N2S = 742.24) 2-2 m/z = 666.84 (C48H30N2S = 666.21)
2-3 m/z = 742.94 (C54H34N2S = 742.24) 2-4 m/z = 742.94 (C54H34N2S =
742.24) 2-5 m/z = 716.90 (C52H32N2S = 716.23) 2-6 m/z = 716.90
(C52H32N2S = 716.23) 2-7 m/z = 783.00 (C57H38N2S = 782.28) 2-8 m/z
= 783.00 (C57H38N2S = 782.28) 2-9 m/z = 772.98 (C54H32N2S2 =
772.20) 2-10 m/z = 772.98 (C54H32N2S2 = 772.20) 2-11 m/z = 756.92
(C54H32N2OS = 756.22) 2-12 m/z = 756.92 (C54H32N2OS = 756.22) 2-13
m/z = 666.84 (C48H30N2S = 666.21) 2-14 m/z = 742.94 (C54H34N2S =
742.24) 2-15 m/z = 742.94 (C54H34N2S = 742.24) 2-16 m/z = 716.90
(C52H32N2S = 716.23) 2-17 m/z = 716.90 (C52H32N2S = 716.23) 2-18
m/z = 783.00 (C57H38N2S = 782.28) 2-19 m/z = 783.00 (C57H38N2S =
782.28) 2-20 m/z = 772.98 (C54H32N2S2 = 772.20) 2-21 m/z = 756.92
(C54H32N2OS = 756.22) 2-22 m/z = 756.92 (C54H32N2OS = 756.22) 2-23
m/z = 772.98 (C54H32N2S2 = 772.20) 2-24 m/z = 666.84 (C48H30N2S =
666.21) 2-25 m/z = 742.94 (C54H34N2S = 742.24) 2-26 m/z = 742.94
(C54H34N2S = 742.24) 2-27 m/z = 783.00 (C57H38N2S = 782.28) 2-28
m/z = 772.98 (C54H32N2S2 = 772.20) 2-29 m/z = 756.92 (C54H32N2OS =
756.22) 2-30 m/z = 772.98 (C54H32N2S2 = 772.20) 2-31 m/z = 783.00
(C57H38N2S = 782.28) 2-32 m/z = 756.92 (C54H32N2OS = 756.22) 2-33
m/z = 666.84 (C48H30N2S = 666.21) 2-34 m/z = 742.94 (C54H34N2S =
742.24) 2-35 m/z = 742.94 (C54H34N2S = 742.24) 2-36 m/z = 772.98
(C54H32N2S2 = 772.20) 2-37 m/z = 756.92 (C54H32N2OS = 756.22) 2-38
m/z = 772.98 (C54H32N2S2 = 772.20) 2-39 m/z = 783.00 (C57H38N2S =
782.28) 2-40 m/z = 756.92 (C54H32N2OS = 756.22) 2-41 m/z = 666.84
(C48H30N2S = 666.21) 2-42 m/z = 742.94 (C54H34N2S = 742.24) 2-43
m/z = 742.94 (C54H34N2S = 742.24) 2-44 m/z = 772.98 (C54H32N2S2 =
772.20) 2-45 m/z = 756.92 (C54H32N2OS = 756.22) 2-46 m/z = 772.98
(C54H32N2S2 = 772.20) 2-47 m/z = 783.00 (C57H38N2S = 782.28) 2-48
m/z = 756.92 (C54H32N2OS = 756.22) 2-49 m/z = 666.84 (C48H30N2S =
666.21) 2-50 m/z = 742.94 (C54H34N2S = 742.24) 2-51 m/z = 742.94
(C54H34N2S = 742.24) 2-52 m/z = 772.98 (C54H32N2S2 = 772.20) 2-53
m/z = 756.92 (C54H32N2OS = 756.22) 2-54 m/z = 772.98 (C54H32N2S2 =
772.20) 2-55 m/z = 783.00 (C57H38N2S = 782.28) 2-56 m/z = 756.92
(C54H32N2OS = 756.22) 2-57 m/z = 666.84 (C48H30N2S = 666.21) 2-58
m/z = 742.94 (C54H34N2S = 742.24) 2-59 m/z = 742.94 (C54H34N2S =
742.24) 2-60 m/z = 772.98 (C54H32N2S2 = 772.20) 2-61 m/z = 756.92
(C54H32N2OS = 756.22) 2-62 m/z = 772.98 (C54H32N2S2 = 772.20) 2-63
m/z = 783.00 (C57H38N2S = 782.28) 2-64 m/z = 756.92 (C54H32N2OS =
756.22) 2-65 m/z = 666.84 (C48H30N2S = 666.21) 2-66 m/z = 742.94
(C54H34N2S = 742.24) 2-67 m/z = 742.94 (C54H34N2S = 742.24) 2-68
m/z = 772.98 (C54H32N2S2 = 772.20) 2-69 m/z = 756.92 (C54H32N2OS =
756.22) 2-70 m/z = 772.98 (C54H32N2S2 = 772.20) 2-71 m/z = 783.00
(C57H38N2S = 782.28) 2-72 m/z = 756.92 (C54H32N2OS = 756.22) 2-73
m/z = 666.84 (C48H30N2S = 666.21) 2-74 m/z = 742.94 (C54H34N2S =
742.24) 2-75 m/z = 742.94 (C54H34N2S = 742.24) 2-76 m/z = 772.98
(C54H32N2S2 = 772.20) 2-77 m/z = 756.92 (C54H32N2OS = 756.22) 2-78
m/z = 772.98 (C54H32N2S2 = 772.20) 2-79 m/z = 783.00 (C57H38N2S =
782.28) 2-80 m/z = 756.92 (C54H32N2OS = 756.22) 2-81 m/z = 666.84
(C48H30N2S = 666.21) 2-82 m/z = 742.94 (C54H34N2S = 742.24) 2-83
m/z = 742.94 (C54H34N2S = 742.24) 2-84 m/z = 772.98 (C54H32N2S2 =
772.20) 2-85 m/z = 756.92 (C54H32N2OS = 756.22) 2-86 m/z = 772.98
(C54H32N2S2 = 772.20) 2-87 m/z = 783.00 (C57H38N2S = 782.28) 2-88
m/z = 756.92 (C54H32N2OS = 756.22) 2-89 m/z = 666.84 (C48H30N2S =
666.21) 2-90 m/z = 742.94 (C54H34N2S = 742.24) 2-91 m/z = 742.94
(C54H34N2S = 742.24) 2-92 m/z = 772.98 (C54H32N2S2 = 772.20) 2-93
m/z = 756.92 (C54H32N2OS = 756.22) 2-94 m/z = 772.98 (C54H32N2S2 =
772.20) 2-95 m/z = 783.00 (C57H38N2S = 782.28) 2-96 m/z = 756.92
(C54H32N2OS = 756.22) 2-97 m/z = 666.84 (C48H30N2S = 666.21) 2-98
m/z = 742.94 (C54H34N2S = 742.24) 2-99 m/z = 742.94 (C54H34N2S =
742.24) 2-100 m/z = 772.98 (C54H32N2S2 = 772.20) 2-101 m/z = 756.92
(C54H32N2OS = 756.22) 2-102 m/z = 772.98 (C54H32N2S2 = 772.20)
2-103 m/z = 783.00 (C57H38N2S = 782.28) 2-104 m/z = 756.92
(C54H32N2OS = 756.22)
Table 21 shows NMR values, and Tables 22 and 23 show measured
values by field desorption mass spectrometry (FD-MS).
FIG. 4 illustrates a measurement graph of LTPL of Compound 1-2 at a
wavelength of 363 nm.
FIG. 5 illustrates a measurement graph of PL of Compound 1-2 at a
wavelength of 238 nm.
FIG. 6 illustrates a UV absorption spectrum of Compound 1-2.
FIG. 7 illustrates a measurement graph of LTPL of Compound 1-11 at
a wavelength of 339 nm.
FIG. 8 illustrates a measurement graph of PL of Compound 1-11 at a
wavelength of 234 nm.
FIG. 9 illustrates a UV absorption spectrum of Compound 1-11.
FIG. 10 illustrates a measurement graph of LTPL of Compound 1-23 at
a wavelength of 241 nm.
FIG. 11 illustrates a measurement graph of PL of Compound 1-23 at a
wavelength of 241 nm.
FIG. 12 illustrates a UV absorption spectrum of Compound 1-23.
FIG. 13 illustrates a measurement graph of LTPL of Compound 1-27 at
a wavelength of 340 nm.
FIG. 14 illustrates a measurement graph of PL of Compound 1-27 at a
wavelength of 241 nm.
FIG. 15 illustrates a UV absorption spectrum of Compound 1-27.
FIG. 16 illustrates a measurement graph of LTPL of Compound 1-33 at
a wavelength of 291 nm.
FIG. 17 illustrates a measurement graph of PL of Compound 1-33 at a
wavelength of 239 nm.
FIG. 18 illustrates a UV absorption spectrum of Compound 1-33.
FIG. 19 illustrates a measurement graph of LTPL of Compound 1-39 at
a wavelength of 259 nm.
FIG. 20 illustrates a measurement graph of PL of Compound 1-39 at a
wavelength of 259 nm.
FIG. 21 illustrates a UV absorption spectrum of Compound 1-39.
FIG. 22 illustrates a measurement graph of LTPL of Compound 1-41 at
a wavelength of 260 nm.
FIG. 23 illustrates a measurement graph of PL of Compound 1-41 at a
wavelength of 260 nm.
FIG. 24 illustrates a UV absorption spectrum of Compound 1-41.
FIG. 25 illustrates a measurement graph of LTPL of Compound 1-65 at
a wavelength of 361 nm.
FIG. 26 illustrates a measurement graph of PL of Compound 1-65 at a
wavelength of 235 nm.
FIG. 27 illustrates a UV absorption spectrum of Compound 1-65.
FIG. 28 illustrates a measurement graph of LTPL of Compound 1-66 at
a wavelength of 360 nm.
FIG. 29 illustrates a measurement graph of PL of Compound 1-66 at a
wavelength of 307 nm.
FIG. 30 illustrates a UV absorption spectrum of Compound 1-66.
FIG. 31 illustrates a measurement graph of LTPL of Compound 1-67 at
a wavelength of 361 nm.
FIG. 32 illustrates a measurement graph of PL of Compound 1-67 at a
wavelength of 266 nm.
FIG. 33 illustrates a UV absorption spectrum of Compound 1-67.
FIG. 34 illustrates a measurement graph of LTPL of Compound 1-69 at
a wavelength of 344 nm.
FIG. 35 illustrates a measurement graph of PL of Compound 1-69 at a
wavelength of 308 nm.
FIG. 36 illustrates a UV absorption spectrum of Compound 1-69.
FIG. 37 illustrates a measurement graph of LTPL of Compound 1-70 at
a wavelength of 344 nm.
FIG. 38 illustrates a measurement graph of PL of Compound 1-70 at a
wavelength of 267 nm.
FIG. 39 illustrates a UV absorption spectrum of Compound 1-70.
FIG. 40 illustrates a measurement graph of LTPL of Compound 1-71 at
a wavelength of 344 nm.
FIG. 41 illustrates a measurement graph of PL of Compound 1-71 at a
wavelength of 241 nm.
FIG. 42 illustrates a UV absorption spectrum of Compound 1-71.
FIG. 43 illustrates a measurement graph of LTPL of Compound 1-78 at
a wavelength of 361 nm.
FIG. 44 illustrates a measurement graph of PL of Compound 1-78 at a
wavelength of 263 nm.
FIG. 45 illustrates a UV absorption spectrum of Compound 1-78.
FIG. 46 illustrates a measurement graph of LTPL of Compound 1-82 at
a wavelength of 344 nm.
FIG. 47 illustrates a measurement graph of PL of Compound 1-82 at a
wavelength of 307 nm.
FIG. 48 illustrates a UV absorption spectrum of Compound 1-82.
FIG. 49 illustrates a measurement graph of LTPL of Compound 1-84 at
a wavelength of 363 nm.
FIG. 50 illustrates a measurement graph of PL of Compound 1-84 at a
wavelength of 298 nm.
FIG. 51 illustrates a UV absorption spectrum of Compound 1-84.
FIG. 52 illustrates a measurement graph of LTPL of Compound 1-99 at
a wavelength of 355 nm.
FIG. 53 illustrates a measurement graph of PL of Compound 1-99 at a
wavelength of 355 nm.
FIG. 54 illustrates a UV absorption spectrum of Compound 1-99.
Experimental Example
Experimental Example 1
1) Manufacture of Organic Light Emitting Device
A glass substrate, in which ITO was thinly coated to have a
thickness of 1,500 .ANG., was ultrasonically washed with distilled
water. When the washing with distilled water is finished, the glass
substrate was ultrasonically washed with a solvent such as acetone,
methanol, and isopropyl alcohol, dried and then was subjected to
UVO treatment for 5 minutes by using UV in a UV washing machine.
Thereafter, the substrate was transferred to a plasma washing
machine (PT), and then was subjected to plasma treatment in a
vacuum state for an ITO work function and in order to remove a
residual film, and was transferred to a thermal deposition
equipment for organic deposition.
As the common layers, the hole injection layer
4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA) and
the hole transport layer
N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine
(NPB) were formed on the ITO transparent electrode (positive
electrode).
A light emitting layer was thermally vacuum deposited thereon as
follows. The light emitting layer was deposited to have a thickness
of 400 .ANG. by using a compound described in the following Table
24 as a host and tris(2-phenylpyridine)iridium (Ir(ppy).sub.3) as a
green phosphorescent dopant to dope the host with Ir(ppy).sub.3 in
an amount of 7%. Thereafter, BCP as a hole blocking layer was
deposited to have a thickness of 60 .ANG., and Alq.sub.3 as an
electron transport layer was deposited to have a thickness of 200
.ANG. thereon. Finally, an organic electroluminescence device was
manufactured by depositing lithium fluoride (LiF) to have a
thickness of 10 .ANG. on the electron transport layer to form an
electron injection layer, and then depositing an aluminum (Al)
negative electrode to have a thickness of 1,200 .ANG. on the
electron injection layer to form a negative electrode.
Meanwhile, all the organic compounds required for manufacturing an
OLED device were subjected to vacuum sublimed purification under
10.sup.-6 to 10.sup.-8 torr for each material, and used for the
manufacture of OLED.
2) Driving Voltage and Light Emitting Efficiency of Organic
Electroluminescence Device
For the organic electroluminescence device manufactured as
described above, electroluminescence (EL) characteristics were
measured by M7000 manufactured by McScience Inc., and based on the
measurement result thereof, T.sub.90 was measured by a lifetime
measurement equipment (M6000) manufactured by McScience Inc. when
the reference brightness was 6,000 cd/m.sup.2. Characteristics of
the organic electroluminescence device of the present invention are
as shown in the following Table 24.
TABLE-US-00024 TABLE 24 Driving voltage Efficiency Color coordinate
(x, Lifetime Compound (V) (cd/A) y) (T.sub.90) Example 1 1-2 4.05
67.2 (0.294, 0.654) 142 Example 2 1-11 3.90 68.9 (0.293, 0.653) 151
Example 3 1-17 3.82 60.5 (0.283, 0.643) 186 Example 4 1-23 4.39
64.1 (0.296, 0.654) 123 Example 5 1-27 4.19 66.1 (0.297, 0.653) 133
Example 6 1-33 4.40 63.2 (0.305, 0.654) 120 Example 7 1-39 3.88
69.9 (0.296, 0.652) 154 Example 8 1-41 4.11 76.6 (0.296, 0.675) 137
Example 9 1-64 4.00 75.6 (0.296, 0.674) 134 Example 10 1-65 3.83
68.3 (0.272, 0.683) 149 Example 11 1-66 4.02 67.1 (0.293, 0.654)
145 Example 12 1-67 3.80 70.2 (0.284, 0.682) 160 Example 13 1-69
4.26 65.4 (0.295, 0.693) 127 Example 14 1-70 4.39 67.0 (0.296,
0.701) 140 Example 15 1-71 4.25 64.7 (0.295, 0.675) 130 Example 16
1-76 4.22 68.7 (0.294, 0.676) 133 Example 17 1-77 3.91 75.5 (0.280,
0.678) 148 Example 18 1-78 3.81 72.5 (0.281, 0.679) 158 Example 19
1-79 3.96 67.2 (0.273, 0.688) 137 Example 20 1-80 3.79 73.1 (0.295,
0.659) 169 Example 21 1-82 3.91 68.2 (0.274, 0.684) 147 Example 22
1-84 3.70 70.1 (0.293, 0.656) 156 Example 23 1-85 3.99 69.2 (0.273,
0.687) 147 Example 24 1-86 3.71 78.1 (0.295, 0.658) 170 Example 25
1-91 3.98 61.2 (0.274, 0.683) 158 Example 26 1-92 3.73 76.1 (0.293,
0.655) 159 Example 27 1-93 3.81 67.6 (0.286, 0.650) 137 Example 28
1-94 4.20 66.7 (0.293, 0.664) 152 Example 29 1-95 3.90 79.2 (0.294,
0.662) 199 Example 30 1-96 3.79 69.3 (0.272, 0.683) 149 Example 31
1-98 3.71 65.3 (0.271, 0.681) 179 Example 32 1-99 4.23 62.7 (0.293,
0.654) 145 Example 33 1-100 3.93 74.2 (0.294, 0.652) 190 Example 34
1-109 3.82 69.4 (0.301, 0.693) 187 Example 35 1-110 4.12 64.4
(0.302, 0.693) 227 Example 36 1-111 3.88 68.9 (0.286, 0.685) 177
Example 37 1-112 3.93 64.9 (0.272, 0.673) 169 Example 38 1-113 4.25
67.7 (0.293, 0.654) 195 Example 39 1-114 3.11 70.2 (0.314, 0.692)
178 Example 40 1-117 3.80 67.5 (0.276, 0.651) 190 Example 41 1-118
3.79 69.3 (0.272, 0.683) 149 Example 42 1-119 4.29 65.1 (0.285,
0.695) 180 Example 43 1-125 3.73 67.0 (0.276, 0.689) 190 Example 44
1-126 4.09 72.5 (0.301, 0.685) 198 Example 45 1-127 3.81 67.6
(0.286, 0.650) 137 Example 46 1-128 3.91 68.2 (0.274, 0.684) 147
Example 47 1-138 3.70 70.1 (0.293, 0.656) 156 Example 48 1-139 4.11
76.6 (0.296, 0.675) 137 Example 49 1-140 4.00 75.6 (0.296, 0.674)
134 Example 50 1-155 3.83 68.3 (0.272, 0.683) 149 Example 51 1-156
4.05 67.2 (0.294, 0.654) 142 Example 52 1-157 3.90 68.9 (0.293,
0.653) 151 Example 53 1-158 3.82 60.5 (0.283, 0.643) 186 Example 54
1-160 3.73 67.0 (0.276, 0.689) 190 Example 55 1-162 3.71 78.1
(0.295, 0.658) 170 Example 56 1-164 3.78 68.9 (0.286, 0.685) 177
Example 57 1-165 4.29 65.1 (0.285, 0.695) 180 Example 58 1-170 4.21
68.2 (0.294, 0.644) 217 Example 59 1-172 3.81 70.1 (0.313, 0.706)
186 Example 60 1-174 3.73 67.0 (0.276, 0.689) 190 Example 61 1-176
3.78 68.9 (0.286, 0.685) 177 Example 62 1-177 3.83 64.9 (0.272,
0.673) 169 Example 63 1-178 4.25 67.7 (0.293, 0.654) 195 Example 64
1-179 3.81 70.2 (0.314, 0.692) 178 Example 65 1-180 3.89 65.4
(0.295, 0.693) 167 Example 66 1-181 3.73 67.0 (0.276, 0.689) 190
Comparative Example 1 CBP 5.23 41.1 (0.285, 0.681) 50 Comparative
Example 2 ref 4 4.82 58.8 (0.294, 0.654) 55 Comparative Example 3
ref 5 4.20 62.3 (0.284, 0.695) 31 Comparative Example 4 ref 6 4.66
61.2 (0.296, 0.676) 80 Comparative Example 5 ref 7 4.10 59.7
(0.276, 0.684) 82 Comparative Example 6 ref 8 4.92 52.2 (0.286,
0.644) 65 Comparative Example 7 ref 9 4.91 56.3 (0.286, 0.644)
73
As can be seen from the results in Table 24, the organic
electroluminescence device using a light emitting layer material of
the organic electroluminescence device of the present invention had
a low driving voltage, an enhanced light emitting efficiency, and a
significantly improved lifetime compared to those in Comparative
Examples 1 to 7.
Meanwhile, when phenylene is positioned between carbazole and
triazine as in Comparative Example 2, the lifetime is reduced
because electrons in the LUMO region fail to be stabilized.
Further, when there is no carbazole as in Comparative Example 3,
the hole mobility deteriorates, and the equilibrium between holes
and electrons in the light emitting layer collapses, thereby
leading to a decrease in lifetime. In addition, in the case of a
compound including dibenzofuran as in Comparative Example 4, the
lifetime is reduced because electrons in the LUMO region fail to be
stabilized. Furthermore, when a substituent is bonded to the 2nd
and 6th positions of dibenzothiophene as in Comparative Example 5,
the equilibrium between holes and electrons in the light emitting
layer collapses, thereby leading to a decrease in lifetime.
Further, as in Comparative Examples 6 and 7, when a heteroaryl
group including at least one N is not bonded to the position of Ar1
of Chemical Formula 1 of the present invention, the equilibrium
between holes and electrons collapses because there is no
substituent which stabilizes electrons, and as a result, a result
of reducing the efficiency or lifetime is obtained.
<Experimental Example 2> Manufacture of Organic Light
Emitting Device
A glass substrate, in which ITO was thinly coated to have a
thickness of 1,500 .ANG., was ultrasonically washed with distilled
water. When the washing with distilled water is finished, the glass
substrate was ultrasonically washed with a solvent such as acetone,
methanol, and isopropyl alcohol, dried and then was subjected to
UVO treatment for 5 minutes by using UV in a UV washing machine.
Thereafter, the substrate was transferred to a plasma washing
machine (PT), and then was subjected to plasma treatment in a
vacuum state for an ITO work function and in order to remove a
residual film, and was transferred to a thermal deposition
equipment for organic deposition.
As the common layers, the hole injection layer
4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA) and
the hole transport layer
N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine
(NPB) were formed on the ITO transparent electrode (positive
electrode).
A light emitting layer was thermally vacuum deposited thereon as
follows. The light emitting layer was deposited to have a thickness
of 400 .ANG. by using a compound described in Chemical Formula 1
and a compound described in Chemical Formula 2 as hosts from the
individual supply source, and was deposited by doping the host with
Ir(ppy).sub.3 as a green phosphorescent dopant in an amount of 7%.
Thereafter, BCP as a hole blocking layer was deposited to have a
thickness of 60 .ANG., and Alq.sub.3 as an electron transport layer
was deposited to have a thickness of 200 .ANG. thereon. Finally, an
organic electroluminescence device was manufactured by depositing
lithium fluoride (LiF) to have a thickness of 10 .ANG. on the
electron transport layer to form an electron injection layer, and
then depositing an aluminum (Al) negative electrode to have a
thickness of 1,200 .ANG. on the electron injection layer to form a
negative electrode.
Meanwhile, all the organic compounds required for manufacturing an
OLED device were subjected to vacuum sublimed purification under
10.sup.-6 to 10.sup.-8 torr for each material, and used for the
manufacture of OLED.
<Experimental Example 3> Manufacture of Organic Light
Emitting Device
A glass substrate, in which ITO was thinly coated to have a
thickness of 1,500 .ANG., was ultrasonically washed with distilled
water. When the washing with distilled water is finished, the glass
substrate was ultrasonically washed with a solvent such as acetone,
methanol, and isopropyl alcohol, dried and then was subjected to
UVO treatment for 5 minutes by using UV in a UV washing machine.
Thereafter, the substrate was transferred to a plasma washing
machine (PT), and then was subjected to plasma treatment in a
vacuum state for an ITO work function and in order to remove a
residual film, and was transferred to a thermal deposition
equipment for organic deposition.
As the common layers, the hole injection layer
4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA) and
the hole transport layer
N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine
(NPB) were formed on the ITO transparent electrode (positive
electrode).
A light emitting layer was thermally vacuum deposited thereon as
follows. The light emitting layer was deposited to have a thickness
of 400 .ANG. by pre-mixing a compound described in Chemical Formula
1 and a compound described in Chemical Formula 2 as hosts, and then
was deposited from one supply source by doping the host with
Ir(ppy).sub.3 as a green phosphorescent dopant in an amount of 7%.
Thereafter, BCP as a hole blocking layer was deposited to have a
thickness of 60 .ANG., and Alq.sub.3 as an electron transport layer
was deposited to have a thickness of 200 .ANG. thereon. Finally, an
organic electroluminescence device was manufactured by depositing
lithium fluoride (LiF) to have a thickness of 10 .ANG. on the
electron transport layer to form an electron injection layer, and
then depositing an aluminum (Al) negative electrode to have a
thickness of 1,200 .ANG. on the electron injection layer to form a
negative electrode.
Meanwhile, all the organic compounds required for manufacturing an
OLED device were subjected to vacuum sublimed purification under
10.sup.-6 to 10.sup.-8 torr for each material, and used for the
manufacture of OLED.
The driving voltages and light emitting efficiencies of the organic
electroluminescence devices according to Experimental Examples 2
and 3 are as follows.
For the organic electroluminescence device manufactured as
described above, electroluminescence (EL) characteristics were
measured by M7000 manufactured by McScience Inc., and based on the
measurement result thereof, T.sub.90 was measured by a lifetime
measurement equipment (M6000) manufactured by McScience Inc. when
the reference brightness was 6,000 cd/m.sup.2.
Characteristics of the organic electroluminescence device of the
present invention are as shown in the following Tables 25 to 27.
For reference, Table 25 is an example in which the two host
compounds in Experimental Example 2 were simultaneously deposited
by using an individual supply source, Table 26 is an example in
which the two light emitting compounds in Experimental Example 3
were pre-mixed, and then deposited by using one supply source, and
Table 27 is an example in which the single host material in
Experimental Example 2 was applied.
##STR00295##
TABLE-US-00025 TABLE 25 Driving Light emitting layer Mixture weight
voltage Efficiency Color coordinate Lifetime compound ratio (V)
(cd/A) (x, y) (T.sub.90) Example 67 1-39:2-2 1:8 4.74 53.2 (0.251,
0.714) 201 Example 68 1:5 4.72 58.2 (0.241, 0.711) 224 Example 69
1:2 4.33 77.2 (0.236, 0.717) 384 Example 70 1:1 4.42 76.8 (0.247,
0.727) 321 Example 71 2:1 4.62 70.2 (0.233, 0.714) 280 Example 72
5:1 4.37 69.3 (0.243, 0.714) 178 Example 73 8:1 4.24 69.0 (0.267,
0.712) 164 Example 74 1-39:2-3 1:2 4.37 73.2 (0.241, 0.711) 373
Example 75 1:1 4.48 72.8 (0.257, 0.729) 319 Example 76 2:1 4.63
71.2 (0.231, 0.714) 271 Example 77 1-40:2-2 1:2 4.36 76.2 (0.241,
0.711) 381 Example 78 1:1 4.49 74.8 (0.247, 0.727) 323 Example 79
2:1 4.64 72.1 (0.253, 0.694) 290 Example 80 1-40:2-3 1:2 4.34 72.2
(0.241, 0.711) 331 Example 81 1:1 4.41 70.8 (0.241, 0.714) 291
Example 82 2:1 4.61 70.2 (0.231, 0.711) 259 Example 83 1-67:2-2 1:2
4.34 77.2 (0.246, 0.717) 379 Example 84 1:1 4.41 76.7 (0.251,
0.714) 311 Example 85 2:1 4.66 73.1 (0.241, 0.711) 279 Example 86
1-67:2-3 1:2 4.44 76.2 (0.246, 0.697) 340 Example 87 1:1 4.51 75.7
(0.247, 0.727) 311 Example 88 2:1 4.96 73.2 (0.223, 0.714) 262
Example 89 1-46:2-2 1:2 4.46 71.2 (0.261, 0.711) 301 Example 90 1:1
4.59 70.7 (0.241, 0.711) 289 Example 91 2:1 4.61 69.1 (0.256,
0.717) 261 Example 92 1-46:2-3 1:2 4.41 70.8 (0.221, 0.691) 291
Example 93 1:1 4.53 69.3 (0.247, 0.727) 269 Example 94 2:1 4.59
68.2 (0.243, 0.714) 252 Example 95 1-41:2-2 1:2 4.46 70.8 (0.267,
0.712) 296 Example 96 1:1 4.60 70.4 (0.241, 0.721) 284 Example 97
2:1 4.61 68.8 (0.252, 0.737) 255 Example 98 1-41:2-3 1:2 4.41 69.3
(0.221, 0.691) 285 Example 99 1:1 4.53 68.8 (0.247, 0.687) 261
Example 100 2:1 4.61 67.2 (0.242, 0.714) 247 Comparative Ref
3:2-2.sup. 1:2 4.31 65.2 (0.251, 0.711) 210 Example 8 Comparative
1:1 4.63 63.3 (0.266, 0.707) 192 Example 9 Comparative 2:1 4.79
61.1 (0.241, 0.691) 182 Example 10 Comparative Ref 3:2-3.sup. 1:2
4.31 64.7 (0.231, 0.721) 199 Example 11 Comparative 1:1 4.63 62.3
(0.266, 0.687) 189 Example 12 Comparative 2:1 4.79 61.2 (0.241,
0.711) 172 Example 13 Comparative .sup. 1-39:Ref 1 1:2 4.33 70.3
(0.246, 0.717) 182 Example 14 Comparative 1:1 4.42 69.6 (0.247,
0.727) 179 Example 15 Comparative 2:1 4.62 68.1 (0.253, 0.694) 162
Example 16 Comparative .sup. 1-39:Ref 2 1:2 4.32 69.7 (0.243,
0.714) 178 Example 17 Comparative 1:1 4.44 68.3 (0.241, 0.711) 174
Example 18 Comparative 2:1 4.45 66.2 (0.241, 0.711) 159 Example 19
Comparative .sup. 1-40:Ref 1 1:2 4.36 69.7 (0.241, 0.691) 177
Example 20 Comparative 1:1 4.49 69.1 (0.257, 0.727) 171 Example 21
Comparative 2:1 4.64 68.3 (0.243, 0.714) 167 Example 22 Comparative
.sup. 1-40:Ref 2 1:2 4.44 68.8 (0.241, 0.714) 166 Example 23
Comparative 1:1 4.45 67.9 (0.241, 0.711) 165 Example 24 Comparative
2:1 4.36 66.6 (0.246, 0.697) 161 Example 25 Comparative .sup.
1-67:Ref 1 1:2 4.46 69.3 (0.266, 0.717) 185 Example 26 Comparative
1:1 4.59 69.2 (0.241, 0.714) 179 Example 27 Comparative 2:1 4.61
68.1 (0.241, 0.711) 171 Example 28 Comparative .sup. 1-67:Ref 2 1:2
4.41 68.6 (0.247, 0.727) 183 Example 29 Comparative 1:1 4.53 67.2
(0.223, 0.694) 175 Example 30 Comparative 2:1 4.59 66.1 (0.241,
0.714) 161 Example 31 Comparative .sup. 1-46:Ref 1 1:2 4.46 69.3
(0.241, 0.711) 180 Example 32 Comparative 1:1 4.59 68.2 (0.251,
0.691) 177 Example 33 Comparative 2:1 4.61 67.1 (0.246, 0.717) 163
Example 34 Comparative .sup. 1-46:Ref 2 1:2 4.61 68.2 (0.251,
0.711) 172 Example 35 Comparative 1:1 4.41 66.4 (0.247, 0.727) 168
Example 36 Comparative 2:1 4.53 65.1 (0.243, 0.694) 161 Example 37
Comparative .sup. 1-41:Ref 1 1:2 4.47 69.1 (0.241, 0.721) 175
Example 38 Comparative 1:1 4.44 67.9 (0.251, 0.693) 172 Example 39
Comparative 2:1 4.63 67.0 (0.246, 0.711) 158 Example 40 Comparative
.sup. 1-41:Ref 2 1:2 4.61 67.7 (0.251, 0.721) 167 Example 41
Comparative 1:1 4.35 66.1 (0.237, 0.737) 163 Example 42 Comparative
2:1 4.56 64.7 (0.243, 0.699) 155 Example 43
TABLE-US-00026 TABLE 26 Driving Light emitting layer Mixture weight
voltage Efficiency Color coordinate Lifetime compound ratio (V)
(cd/A) (x, y) (T.sub.90) Example 101 1-39:2-2 1:8 4.72 53.7 (0.253,
0.714) 234 Example 102 1:5 4.68 58.9 (0.241, 0.691) 252 Example 103
1:2 4.33 77.2 (0.256, 0.717) 513 Example 104 1:1 4.42 76.8 (0.247,
0.727) 451 Example 105 2:1 4.62 70.2 (0.243, 0.714) 413 Example 106
5:1 4.37 69.3 (0.257, 0.737) 286 Example 107 8:1 4.24 69.0 (0.243,
0.732) 262 Example 108 1-39:2-3 1:2 4.37 73.2 (0.241, 0.691) 401
Example 109 1:1 4.48 72.8 (0.257, 0.729) 449 Example 110 2:1 4.63
71.2 (0.241, 0.714) 401 Example 111 1-40:2-2 1:2 4.36 76.2 (0.241,
0.711) 507 Example 112 1:1 4.49 74.8 (0.247, 0.727) 453 Example 113
2:1 4.64 72.1 (0.233, 0.714) 423 Example 114 1-40:2-3 1:2 4.34 72.2
(0.241, 0.691) 461 Example 115 1:1 4.41 70.8 (0.241, 0.714) 423
Example 116 2:1 4.61 70.2 (0.231, 0.711) 381 Example 117 1-67:2-2
1:2 4.34 77.2 (0.246, 0.717) 503 Example 118 1:1 4.41 76.7 (0.241,
0.694) 440 Example 119 2:1 4.66 73.1 (0.231, 0.711) 409 Example 120
1-67:2-3 1:2 4.44 76.2 (0.246, 0.717) 470 Example 121 1:1 4.51 75.7
(0.247, 0.727) 455 Example 122 2:1 4.96 73.2 (0.253, 0.714) 396
Example 123 1-46:2-2 1:2 4.46 71.2 (0.241, 0.691) 430 Example 124
1:1 4.59 70.7 (0.241, 0.711) 413 Example 125 2:1 4.61 69.1 (0.236,
0.717) 396 Example 126 1-46:2-3 1:2 4.41 70.8 (0.241, 0.711) 421
Example 127 1:1 4.53 69.3 (0.257, 0.727) 393 Example 128 2:1 4.59
68.2 (0.243, 0.694) 382 Example 129 1-41:2-2 1:2 4.46 70.7 (0.241,
0.693) 425 Example 130 1:1 4.62 70.2 (0.241, 0.721) 408 Example 131
2:1 4.65 68.8 (0.236, 0.717) 391 Example 132 1-14:2-3 1:2 4.41 70.2
(0.241, 0.711) 415 Example 133 1:1 4.55 69.0 (0.257, 0.737) 387
Example 134 2:1 4.60 67.9 (0.243, 0.732) 377 Example 135 1-39:2-7
1:2 4.32 70.2 (0.263, 0.704) 425 Example 136 1:1 4.46 72.5 (0.251,
0.683) 386 Example 137 1-39:2-9 1:2 4.42 65.4 (0.271, 0.701) 395
Example 138 1:1 4.63 67.2 (0.266, 0.697) 369 Example 139 1-39:2-11
1:2 4.72 67.5 (0.271, 0.705) 415 Example 140 1:1 4.85 69.4 (0.267,
0.682) 387 Example 141 1-46:2-7 1:2 4.46 64.2 (0.263, 0.662) 432
Example 142 1:1 4.69 65.5 (0.253, 0.672) 385 Comparative Ref
3:2-2.sup. 1:2 4.31 65.2 (0.241, 0.711) 250 Example 44 Comparative
1:1 4.63 63.3 (0.256, 0.697) 241 Example 45 Comparative 2:1 4.79
61.1 (0.241, 0.711) 234 Example 46 Comparative Ref 3:2-3.sup. 1:2
4.31 64.7 (0.231, 0.711) 243 Example 47 Comparative 1:1 4.63 62.3
(0.246, 0.717) 233 Example 48 Comparative 2:1 4.79 61.2 (0.251,
0.691) 220 Example 49 Comparative .sup. 1-39:Ref 1 1:2 4.33 70.3
(0.246, 0.717) 249 Example 50 Comparative 1:1 4.42 69.6 (0.247,
0.727) 229 Example 51 Comparative 2:1 4.62 68.1 (0.243, 0.694) 221
Example 52 Comparative .sup. 1-39:Ref 2 1:2 4.32 69.7 (0.233,
0.714) 231 Example 53 Comparative 1:1 4.44 68.3 (0.241, 0.711) 221
Example 54 Comparative 2:1 4.45 66.2 (0.241, 0.691) 213 Example 55
Comparative .sup. 1-40:Ref 1 1:2 4.36 69.7 (0.231, 0.711) 235
Example 56 Comparative 1:1 4.49 69.1 (0.247, 0.727) 220 Example 57
Comparative 2:1 4.64 68.3 (0.243, 0.714) 210 Example 58 Comparative
.sup. 1-40:Ref 2 1:2 4.44 68.8 (0.251, 0.694) 234 Example 59
Comparative 1:1 4.45 67.9 (0.241, 0.711) 221 Example 60 Comparative
2:1 4.36 66.6 (0.246, 0.717) 215 Example 61 Comparative .sup.
1-67:Ref 1 1:2 4.46 69.3 (0.236, 0.697) 229 Example 62 Comparative
1:1 4.59 69.2 (0.241, 0.714) 215 Example 63 Comparative 2:1 4.61
68.1 (0.251, 0.711) 210 Example 64 Comparative .sup. 1-67:Ref 2 1:2
4.41 68.6 (0.247, 0.727) 245 Example 65 Comparative 1:1 4.53 67.2
(0.243, 0.694) 234 Example 66 Comparative 2:1 4.59 66.1 (0.241,
0.714) 229 Example 67 Comparative .sup. 1-46:Ref 1 1:2 4.46 69.3
(0.251, 0.711) 241 Example 68 Comparative 1:1 4.59 68.2 (0.241,
0.691) 235 Example 69 Comparative 2:1 4.61 67.1 (0.246, 0.717) 221
Example 70 Comparative .sup. 1-46:Ref 2 1:2 4.61 68.2 (0.241,
0.711) 231 Example 71 Comparative 1:1 4.41 66.4 (0.237, 0.727) 227
Example 72 Comparative 2:1 4.53 65.1 (0.243, 0.714) 219 Example 73
Comparative .sup. 1-41:Ref 1 1:2 4.49 69.0 (0.221, 0.721) 236
Example 74 Comparative 1:1 4.62 67.9 (0.231,0.621) 230 Example 75
Comparative 2:1 4.63 66.6 (0.256, 0.727) 216 Example 76 Comparative
.sup. 1-41:Ref 2 1:2 4.64 67.7 (0.251, 0.731) 225 Example 77
Comparative 1:1 4.43 66.0 (0.257, 0.697) 222 Example 78 Comparative
2:1 4.55 64.7 (0.243, 0.694) 214 Example 79
TABLE-US-00027 TABLE 27 Driving Light emitting layer voltage
Efficiency Color coordinate Lifetime compound (V) (cd/A) (x, y)
(T.sub.90) Comparative 2-2 4.75 51.2 (0.254, 0.724) 121 Example 80
Comparative 2-3 4.83 50.9 (0.233, 0.703) 112 Example 81 Comparative
Ref 1 4.83 52.4 (0.258, 0.727) 95 Example 82 Comparative Ref 2 4.93
51.5 (0.247, 0.737) 83 Example 83 Comparative Ref 3 4.81 55.9
(0.246, 0.727) 104 Example 84
The organic light emitting device of the present invention includes
a light emitting layer which uses a host and a phosphorescent
dopant, and the host is composed of a host compound (p-n type) in
which two or more compounds are mixed, and as a result, the organic
light emitting device of the present invention has better lifetime
characteristics than an organic light emitting device including a
host compound composed of a single compound in the related art.
In particular, the p-n type host of the present invention has an
advantage in that the ratio of the host may be adjusted to increase
the light emitting characteristics, and the advantage is a result
which can be achieved by appropriately combining a P host having a
good hole mobility and an n host having a good electron
mobility.
Further, in the present invention, the light emitting host composed
of plural species of compounds was deposited by pre-mixing
mixtures, and then forming the host by one deposition supply
source. In this case, since the deposition is not conducted several
times, the uniformity and thin film characteristics of the thin
film may be improved, the process procedures may be simplified, the
costs may be reduced, and a device in which the efficiency and
lifetime have been improved may be formed.
* * * * *